Controlled delivery compositions and processes for treating organisms in a column of water on land

ABSTRACT

Controlled release compositions of matter are disclosed comprising complexes for treating a population of ore or more aquatic organisms in a column of water. The complexes comprise a least one system wherein the system comprises at least one bioactive agent as a component selected for treating a population of aquatic organisms, at least one carrier component, and at least one coating component for regulating the controlled release rate and release profile of the bioactive agent in water or at least one bioactive agent and one joint-function component that can serve as both a carrier and coating to regulate the controlled release rate and release profile of the bioactive agent in water, with or without optional binder components and/or additional formulation materials. The components are selected to sink or float so that the complexes will permeate and/or remain in any planar or volumetric segment of a water column for a period of time that is sufficient to effectively treat a population of aquatic organisms. Methods for treating a column of water are also disclosed which comprises delivering the compositions to a column of water or to a dry preflood area (pretreatment) that will develop in a column of water or a flood area. The composition and process can also be used to treat terrestrial organisms.

This application is a division of application Ser. No. 08/674,813 U.S.Pat. No. 6,001,382, filed Jul. 3, 1996, which continuation in partapplication of U.S. patent application Ser. No. 08/434,313 filed, May 2,1995, which is a continuation in part application of Ser. No.08/409,301, filed Mar. 24, 1995, which is a continuation in partapplication of U.S. patent application Ser. No. 08/406,344 filed Mar.17, 1995, all of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of Invention

The present invention is directed to compositions and processes forcontrolled delivery of bioactive agents to a population of aquaticorganisms located in any planar or volumetric segment of a column ofwater by ground or aerial application techniques. Organisms of specialinterest are disease-carrying or biting or non-biting nuisance insects,and parasitic animals or plants, especially weeds. Compositions forcontrolled delivery of bioactive agents to terrestrial organisms arealso described.

2. Description of Related Art

Various methods have been devised for delivering biologically activematerials to control pests and vegetation. For example, Yaffe et al.,U.S. Pat. No. 3,274,052 describes a process and a composition in whichmolten droplets of a normally solid toxicant are sprayed on the surfaceof a granular carrier whereupon they adhere to and solidify on thesurface of the carrier as an adherent coating. When employed fortreating aquatic environments, the specific gravity of the granules, andthe rate of release of the toxicant is adjusted during the manufactureto provide surface, intermediate or bottom contact, or penetration intomud to control the specific organisms involved. Neither methods norcompositions are described for adjusting the specific gravity.

Hedges et al., U.S. Pat. No. 3,917,814, describes a nonpoisonousinsecticidal composition consisting of diatomaceous earth having asorptive silica gel adhered to the surface.

Jacobson et al., U.S. Pat. No. 5,180,585, describes an antimicrobialcomposition consisting of inorganic core particles coated with a metalor metal compound having antimicrobial properties.

Thies et al., U.S. Pat. No. 4,464,317, describes a process forencapsulating a pesticide with an inorganic silicate coating. Theencapsulated materials according to the inventors are capable offragmenting upon storage in water to provide controlled release of apesticide such as a mosquito control agent. Non-encapsulated materialswere shown to have about half the active life of-the encapsulatedmaterials.

Levy, U.S. Pat. Nos. 4,818,534; 4,983,389; 4,983,390; and 4,985,251,describe various insecticidal, herbicidal, terrestrial, and flowableinsecticidal delivery compositions based on bioactive materials andsuperabsorbent polymers.

One of the problems encountered in delivering bioactive materials toaquatic environments is that the aquatic organism to be treated is notimmediately susceptible to being contacted with the bioactive materialbecause of its location in a column of water either at the surface, thebottom, or some intermediate region in between. Because of the specificgravity of the bioactive material, in many instances it cannot betargeted to precisely treat the organisms of interest in the watercolumn. By way of example, bioactive materials that have a specificgravity greater than water will generally be ineffective for treatingaquatic organisms at the surface of a column, and vice-versa. Aquaticorganisms that persist at some intermediate level are also difficult totreat for the same reason.

The foregoing illustrates that various delivery systems have beendevised for bioactive materials, and the need to have a controlleddelivery system suitable for delivering these materials to aquaticorganisms. Although there is some suggestion that by adjusting thespecific gravity of a toxicant composition of matter, it would besuitable for delivering the toxicant to an aquatic environment either atthe surface, the bottom or at some intermediate level, the means foradjusting the specific gravity have not been disclosed.

Accordingly, the present invention is directed to compositions andprocesses for treating a population of one or more aquatic organisms ina column of water in which the foregoing and other disadvantages areovercome.

The present invention is also directed to compositions and processes forpretreating a dry (preaquatic) habitat area before it has been floodedby rain or tides, and which is a breeding site for the target aquaticorganism(s), i.e. a preflood area. Pretreating a flooded aquatic habitatarea before the target aquatic organism(s) breed is also within thescope of the invention, as well as flooded habitats where the organismsexist.

The foregoing illustrates that various delivery systems have beendevised for bioactive materials, and the need to have a controlleddelivery system suitable for delivering these materials to one or moreterrestrial organisms, i.e. non-aquatic organisms. Although there aresome systems that are available to provide control of these organisms,it would be advantageous to provide additional compositions foraddressing the problems caused by such organisms whether they are plant,insect, or other animal pests.

Accordingly, the present invention is directed to compositions andprocesses for treating one or more terrestrial organisms in which theforegoing and other disadvantages are overcome.

Specifically, the advantages sought to be obtained according to thepresent invention are to provide compositions of matter or processes fortreating a population of one or more aquatic organisms in a column ofwater, or one or more terrestrial organisms. Throughout thespecification it is intended that the terms “treat,” “treating,” or“treatment” are intended to mean such things as enhancing development ofan organism, prolonging life of an organism, stopping or reversing thedevelopment of a condition in an organism, stopping the development ofan organism, eliciting a response from an organism, protecting anorganism or eradicating an organism.

SUMMARY OF INVENTION

These and other advantages are realized by the present invention whichcomprises compositions of matter and processes which substantiallyobviates one or more of the limitations and disadvantages of the relatedart.

Additional features and advantages of the invention will be set forth inthe written description which follows, and in part will be apparent fromthis description, or may be learned by practice of the invention. Theobjectives and other advantages of the invention will be realized andattained by the compositions of matter and processes particularlypointed out in the written description and claims hereof.

To achieve these and other advantages, and in accordance with thepurpose of the invention, as embodied and broadly described, theinvention comprises compositions of matter for treating an aquaticcolumn of water comprising a bioactive agent as a component for treatinga population of one or more aquatic organisms, a carrier component, anda coating component for regulating the controlled release rate (i.e.fast, slow, pulsed or delayed), and release profile (i.e. zero-order,first-order, and square-root-of-time kinetics) of the bioactive agent inwater. The compositions of matter of the invention can optionally becombined with a binder component to aid in agglomerating thecompositions, or a variety of formulation ingredients to enhance theperformance of the compositions.

Compositions of matter are also described for treating a population ofone or more aquatic organisms in a column of water comprising abioactive agent as a component for treating a population of one or moreaquatic organisms, and a joint-function carrier component that not onlycarries the bioactive material but also is a coating component forregulating the controlled release rate, and release profile of thebioactive agent in water. The compositions of matter of the inventioncan optionally be combined with a binder component to aid inagglomerating the compositions, or a variety of formulation ingredientsto enhance the performance of the compositions.

Further in this regard, a composition of matter is provided comprising acomplex for treating a population of one or more aquatic organisms in acolumn of water, the complex comprising at least one controlled deliverysystem wherein the controlled delivery system comprises at least onebioactive agent as a component for treating a population of one or moreaquatic organisms, at least one carrier component, at least one coatingcomponent for regulating the controlled release rate, and releaseprofile of the bioactive agent in water, with or without one or morebinder component(s) for agglomerating said composition into larger unitssuch as granules, pellets, and briquets, or additional formulationingredients.

In another complex, the controlled delivery system comprises at leastone bioactive agent as a component for treating a population of aquaticorganisms, at least one joint-function carrier component that is also acoating component for regulating the controlled release rate, andrelease profile of the bioactive agent in water, with or without one ormore binder components for agglomerating said composition into largerunits such as granules, pellets, and briquets, or additional formulationingredients.

In yet another complex, the controlled delivery system comprises atleast one bioactive agent as a component for treating a population ofone or more aquatic organisms, at least one joint-function carriercomponent that is also a coating component for regulating the controlledrelease rate, and release profile of the bioactive agent in water, atleast one additional component such as an additional coating componentto further regulate or modify the controlled release rate, and releaseprofile of the bioactive agent in water, with or without one or morebinder components for agglomerating said composition into larger unitssuch as granules, pellets, and briquets, or additional formulationingredients.

The components are selected to sink or float so that each complex orcomposition will permeate, and remain in any planar or volumetricsegment of a water column for a period of time sufficient to effectivelytreat a population of one or more aquatic organisms.

A method is also provided in which the foregoing compositions aredelivered to the column of water in order to time-release the bioactiveagent(s) in the water so as to make it available to treat the aquaticorganisms.

The invention also comprises compositions of matter for treating one ormore terrestrial organisms comprising a bioactive agent as a componentfor treating a population of one or more terrestrial organisms, anoptional carrier component, and a coating component for regulating thecontrolled release rate, and release profile of the bioactive agent.These compositions of matter of the invention can optionally be combinedwith a binder component to aid in agglomerating the compositions, or avariety of formulation ingredients to enhance the performance of thecompositions.

Compositions of matter are also described for treating a population ofone or more terrestrial organisms comprising a bioactive agent as acomponent for treating a terrestrial organism, and a joint-functioncarrier component that not only carries the bioactive material but alsois a coating component for regulating the controlled release rate, andrelease profile of the bioactive agent. The compositions of matter ofthe invention can optionally be combined with a binder component to aidin agglomerating the compositions, or a variety of formulationingredients to enhance the performance of the compositions.

Further in this regard, a composition of matter is provided comprising acomplex for treating a population of one or more terrestrial organisms,the complex comprising at least one controlled delivery system whereinthe controlled delivery system comprises at least one bioactive agent asa component for treating a terrestrial organism, at least one optionalcarrier component, at least one coating component for regulating thecontrolled release rate, and release profile of the bioactive agent,with or without one or more binder component(s) for agglomerating saidcomposition into larger units such as granules, pellets, and briquets,or additional formulation ingredients.

In another complex, the controlled delivery system comprises at leastone bioactive agent as a component for treating a population of one ormore terrestrial organisms, at least one joint-function carriercomponent that is also a coating component for regulating the controlledrelease rate, and release profile of the bioactive agent, with orwithout one or more binder components for agglomerating said compositioninto larger units such as granules, pellets, and briquets, or additionalformulation ingredients.

In yet another complex, the controlled delivery system comprises atleast one bioactive agent as a component for treating a population ofone or more terrestrial organisms, at least one joint-function carriercomponent that is also a coating component for regulating the controlledrelease rate, and release profile of the bioactive agent, at least oneadditional component such as an additional coating component to furtherregulate or modify the controlled release rate, and release profile ofthe bioactive agent, with or without one or more binder components foragglomerating said composition into larger units such as granules,pellets, and briquets, or additional formulation ingredients.

A method is also provided in which the foregoing compositions aredelivered to a terrestrial environment in order to time-release thebioactive agent(s) so as to make it available to treat the terrestrialorganisms. The terrestrial environment is one that is a habitat orpotential habitat for the terrestrial organisms.

It is understood that both the foregoing general description and thefollowing detailed description are exemplary, and explanatory, andfurther, the following description is intended to provide a moredetailed explanation of the invention as claimed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of a porous, or degradable container, suchas a water soluble polyvinyl alcohol pouch or film containing thecomposition of the present invention; and

FIG. 2 is a perspective view of a dispensing container having aperturesfor dispensing the composition of the present invention to an aquatic orterrestrial habitat.

DETAILED DESCRIPTION

The effectiveness of bioactive materials, especially on aquaticorganisms, is generally dependent on delivery of the material to thespecific organisms that are targeted for treatment, i.e., effectivenessis dependent on the bioavailability of the material which can beproblematic in aqueous environments. For example, some bioactivematerials when delivered to an aqueous environment will not remain inthe region of interest, where the aquatic organisms are located, for alength of time sufficient to provide complete treatment of the organism.This is generally remedied by several successive treatments which iscostly in terms of the labor and machinery expenses incurred in multipleapplications.

An example would be the use of a bioactive material having a specificgravity greater than one, used for the treatment of aquatic organismsthat persisted at the surface of a body of water.

Similar problems would also occur where the bioactive material has aspecific gravity less than one, and the aquatic organisms have a habitatbeneath the surface of, or at the bottom of a body of water. In thiscase, the bioactive material could be injected by means of a tube orother device beneath the surface of the water, but since it has aspecific gravity less than one, it would not persist in the region whereit is delivered, and would also require multiple applications in orderto be effective.

In order to overcome these difficulties, compositions and processes havebeen provided for treating a column of water where compositions can bespecifically formulated to persist either at the top or the bottom ofthe column or at any planar or volumetric segment in between the top andthe bottom.

One composition of matter of the present invention is based on at leastone bioactive agent for treating a population of one or more aquaticorganisms, at least one carrier component, and at least one coatingcomponent for regulating the controlled release rate, and releaseprofile of the bioactive agent in water, with or without one or morebinder components for agglomerating said composition into larger unitssuch as granules, pellets, and briquets, or additional formulationingredients.

A second composition of matter is based on at least one bioactive agentfor treating a population of one or more aquatic organisms, at least onejoint-function carrier component that is also a coating component forregulating the controlled release rate, and release profile of thebioactive agent in water, with or without one or more binder componentsfor agglomerating said composition into larger units such as granules,pellets, and briquets, or additional formulation ingredients.

A third composition of matter is based on at least one bioactive agentfor treating a population of one or more aquatic organisms, at least onejoint-function carrier component that is also a coating component forregulating the controlled release rate, and release profile in water,and at least one additional component such as an additional coatingcomponent to further regulate or modify the controlled release rate, andrelease profile of the bioactive agent in water, with or without one ormore binder components for agglomerating said composition into largerunits such as granules, pellets, and briquets, or additional formulationingredients.

In another embodiment, the invention relates both to a composition andprocess for treating a population of one or more terrestrial organisms.This comprises delivering to a terrestrial environment, a composition ofmatter comprising a complex for treating a population of one or moreterrestrial organisms, the complex comprising at least one controlleddelivery system wherein the controlled delivery system comprises anoptional carrier component, at least one bioactive agent as a componentselected for treating a population of one or more terrestrial organisms,and at least one high molecular weight organic plasticizer coatingcomponent for regulating the controlled release rate and release profileof the bioactive agent. The components are selected so the complex willremain in an application site for a period of time sufficient toeffectively treat a population of one or more terrestrial organisms.

The various components are selected to sink or float so that myeachcomplex or composition will permeate, and remain in any planar orvolumetric segment of a water column for a period of time sufficient toeffectively treat a population of one or more aquatic organisms.

The aforementioned compositions of matter of the present invention canbe placed in one or more differentially water soluble, flexible orrigid, porous, or degradable or biodegradable packets, pouches,capsules, canisters, extrusions, coatings, and the like, of polyvinylalcohol, polyethylene oxide, and hydroxypropyl methyl cellulose films ofvarious thicknesses (e.g., 1-3 mil) to further modify the coatingregulated controlled release rate, and release profile of the bioactiveagent(s) formulated in the powdered, granulated or agglomeratedcompositions.

Furthermore, the controlled release rate, and release profile of one ormore bioactive agents from all compositions of matter of the presentinvention can be optionally modified by placing said compositions (i.e.,liquid, powdered, or granular or agglomerated) into various shaped(e.g., spherical, cylindrical, etc.) disposable or reusable,,biodegradable, porous, or degradable or nondegradable, dispensers (e.g.,plastic or metal) such as water soluble polyvinyl alcohol pouch 10having a continuous outer wall 12 that envelops the composition of theinvention therein (not illustrated). or metal container 14 having outerwall 16 and bottom wall 18 and 20, with one or more orifices (e.g.,holes, slots, etc.) 22 and 24 through which the bioactive agentformulation therein (not illustrated) will be delivered.

Dispensing devices can be of various densities for use in aqueousenvironments, and can be anchored in various surface, and/or subsurfacelocations of an aquatic habitat or can be freely dispensed to float,and/or sink at will. These optional dispensing devices can also beutilized in pretreatment or dry aquatic habitats that are scheduled tobecome aquatic e.g. by the advent of rain, and/or tides.

The carrier comprises a material that will float or sink, and is basedon either inorganic or organic compounds that are hydrophobic orhydrophilic. Carriers can be any natural or synthetic material of anysize, shape or texture and can be particulate such as powders granules,pellets, briquets or agglomerated or continuous in the form ofextrusions, films, sheets or laminates.

Carriers can be porous or non-porous, rigid, semi-rigid flexible orelastic. Non-limiting examples of carriers include special interestmaterials such as silica (including sand and diatomaceous earth),cellulose fibers such as PRE-CO-FLOC® which is derived from purifiedvirgin wood pulp, which is fully bleached in a sulfite pulp processhaving an average fiber length of from about 50 to about 90 microns, anda thickness of from about 7 to 30 microns, metal oxides, clays, paper,infusorial earth, slag, or lava, all of which may be finely ground orhave a small particle size, but can be agglomerated into largercomponents with the addition of a binder component. Hydrophilicmaterials that have been surface treated to be hydrophobic, e.g., by asilicone coating are also suitable. Other carriers can include filmssheets, or extrusions of polyvinyl alcohol, polyethylene oxide, andhydroxy propyl methyl cellulose, MONO-SOL® LXP-1832 which is a FDAapproved hydroxypropyl methyl cellulose (MHPC) and is edible, MONO-SOL®PXPN-1257 MHPC, and the MONO-SOL® 6000, 7000 and 8000 series which arepolyvinyl alcohol polymer or copolymer films, other polymer sheets,extrusions or films noted herein, thermolytically processed hydrophobic“pin chips” (waste wood, or saw dust) (Sea Sweep®), cetyl alcohol,stearyl alcohol, vermiculite, ground cork, corn cobs, bagasse from sugarcane or grapes and the like, seed, seed hulls from any cereal crop, suchas rice, rice hulls, oats, oat hulls, wheat, wheat hulls, barley, barleyhulls and the like, paper, and especially dust free paper granules suchas BIODAC®, manufactured from recycled, cellulosic based paper waste andcontaining from about 47 to about 53wt. % paper fiber, from about 28 toabout 34 wt. % clay, and especially paper grade clays or mixturesthereof, including Kaolin, about 14 to about 20 wt. % calcium carbonateor art known equivalents thereof and mixtures thereof, and from about0.01 to about 0.9 wt. % of an inorganic pigment such as titaniumdioxide, or the art known equivalents thereof, and mixtures thereof.Other materials that may be employed as carriers include carbonmaterials such as charcoal, petroleum coke, coke from coal, CVD carbon,carbon black, lamp black, activated carbon, and graphite, rubber,gypsum, cement, concrete, asphalt, wood, fiber glass, glass, metals,metal alloys, clothing fabrics, plaster of Paris, mineral aggregate,leather, natural and synthetic fibers, liposomes, lipospheres, foodproteins, such as zein and its equivalents, polymeric materials, such asolefinic polymer materials, e.g., homopolymers, and/or copolymers ofpolyethylene or polypropylene, fluorinated polymers such aspolytetrafluoroethylene, or polyvinylidene fluoride, or chlorinatedpolymers such as polyvinyl chloride homopolymers and copolymers,acrylate polymers such as acrylic acid and alkyl acrylic acids or estersor amides including the homopolymers and copolymers thereof, and thelike. Polysaccharides can also be employed as carriers includingstarches and modified starches, especially as both are described herein,carrageenan, algin, which is intended to include alginates as well,xanthates, and agar.

The carriers take any shape or form, including agglomerates, granules,pellets, briquets, fibers, fabrics, continuous sheets, discontinuoussheets, films, extruded rods, tubes, whether circular or multi-walledsuch as triangular, square, and the like. The carriers therefore presentany surface for coating whether a continuous or a discontinuous surface.Granules, pellets, or briquets comprise especially suitable carriershapes and sizes although other shapes find use such as powders andsimilar particulate configurations. The carriers can be combined toalter or enhance the performance characteristics of a composition, two,three or four carriers being especially suitable in this regard.

The especially preferred materials in this regard can comprise silicasand silicates.

Precipitated silicas employed in this regard are produced from solutionsof water glass into which sulfuric acid is introduced under fixedconditions. They are formed in the aqueous phase, and depending on theconditions of precipitation, it is possible to produce products withsmaller or somewhat larger primary particles, which then basicallydetermine particle size and specific. surface area. The precipitatesobtained are then washed and dried by methods known in the art.

Silicates are also manufactured by a precipitation method, however, theacids which are necessary for precipitation are replaced partially orcompletely by solutions of metallic salts such as aluminum sulfate, andthe like. The precipitation parameters can also be adjusted to suit thevarious raw materials.

The silicas obtained in this way can be dried by a spray dryingtechnique to obtain particles that are substantially spherical, have asize anywhere from about 50 to about 150 μm, and have excellent flowproperties.

Spray dried precipitated silicas may also be ground so that thedensities will vary anywhere from about 80 g/l to about 270 g/l, and theparticle size anywhere from about 4 μm to 100 μm.

Precipitated silicas and silicates can also be dried by standard dryingprocesses, for example in turbo-driers or rotating driers. Silicas andsilicates dried in this conventional way must always be subsequentlyground. The average particle size and the tapped density also depend onthe degree of grinding. The tapped density in this regard can be fromabout 80 g/l to about 240 g/l, and the particle size from about 4 μm toabout 15 μm.

Silicas can also be produced by means of a high temperature flamehydrolysis during which silicon tetrachloride is hydrolyzed in anoxyhydrogen flame, which is sometimes referred to as pyrogenic silica.The tapped density of these silicas is somewhere around 50 g/l. Both theprecipitated silicas and the pyrogenic silicas can be after-treated in asecondary stage in order to change the naturally hydrophilic surface toa hydrophobic surface e.g. by a suitable chlorosilane to react with asilanol group on the surface of the silica.

The silicas and silicates are further described in Technical BulletinPigments, Synthetic Silicas For Plant Protection and Pest Control, No. 1Degussa, Pig. 27-6-2-79OME, 5th Ed., Date of Issue: Jul. 19, 1990,CAB-0-SIL® FUMED SILICAS, TD-117 7M/11/92, Copyright 1990 CabotCorporation, and Bergna, The Colloid Chemistry of Silica, ACS, 1994 allof which are incorporated herein by reference.

Silicas that are especially suitable, include both the hydrophilic andthe hydrophobic silicas which have been treated with a chlorosilane, andgenerally have a surface area of from about 50 to 450 m²/g, an averageagglomerate size of from about 3.5 to about 100 μm, or an averageprimary particle size of from about 12 to 30 nm, a tapped density offrom about 50 to 240 g/l, a pH of from about 3.6 to about 9, and a DBPadsorption of about 160 to 335 g/100 g.

The silicates that may be employed in this regard comprise those thathave a surface area from about 30 to about 40 m²/g, an averageagglomerate size of from about 4 to about 6 μm, a tapped density of fromabout 285 to 315 g/l, a pH of from about 9.5 to about 10.5, and a DBPadsorption of from about 150 to about 170 g/100 g.

The other inorganic carriers and some of the polymeric organic carriersnoted in this regard will also have substantially the same surface areaand particle size, although the density will vary depending upon thematerial employed. Larger surface areas and particle sizes can also beutilized. Extruded films that are water-soluble can also be effectivecarriers in certain formulations. Other carriers that may be employedare described by Stilman, Immobilization On Polymers, 1983 which isincorporated herein by reference.

The various bioactive agents that are employed in the compositions ofthe present invention to treat populations of adult or immature (e.g.,egg, larvae, pupae, nymphs) organisms comprise technical or formulated(technical plus inerts) pesticides, insecticides, toxicants,monomolecular surface films, petroleum oils, insect growth regulators,plant growth regulators, animal growth regulators, microbial controlagents, pharmaceuticals, medicaments, antibiotics, pathogens, bioactivecontrol agents, parasites, pharmaceuticals or medicaments, bactericides,and viricides, fungicides, algaecides, herbicides, nematicides,amoebicides, acaricides, miticides, predicides, schistisomicides,molluscicides, larvicides, pupicides, ovicides, adulticides,nymphicides, attractants, repellents, growth stimulants, feedingstimulants, nutrients, hormones, chemosterilants, or pheromones,fragrances, flavorants, food additives and combinations thereof, such asthe two, three or four component combinations. Two or more bioactiveagents can be combined in the same composition to achieve multifunctional performance from a single application.

Insecticidal bioactive materials include Bacillus thuringiensis, andespecially subspecies kurstaki and israelensis, Bacillus sphaericus,Bacillus popilliae, Seriatia marcescens, and Lagenidium giganteum, whichare sometimes referred to as bioactive agents employed for the controlof insects. Fungal larvicides may also be employed such as Lagenidiumgiganteum mycelium or Lagenidium giganteum oospores or mixtures thereof.Pyrethrin and pyrethroid larvicides can also be used. Fungal materialscan also be effective against mosquito larvae. Insect growth regulatorscan be used such as (S)-methoprene, diflubenzuron, or pyriproxyfen.Aliphatic petroleum hydrocarbons may also be used as mosquito larvicidesor non-petroleum hydrocarbon oils that form a monomolecular film on thewater to be treated. Compositions and processes for control of variousspecies of mosquitoes, and other pest dipterans in aquatic habitats areof particular interest. Bioactive agents of specific interest for use inthese compositions include Bacillus thuringiensis var. israelensis,Bacillus sphaericus, Lagenidiurm giganteum, methoprene, diflubenzuron,pyriproxyfen, temephos, 2 mol ethoxylate of isostearyl alcohol,lecithins, and petroleum oils, and combinations thereof, such as thetwo, three or four component combinations. Other insecticides may alsobe employed including products such as malathion, resmethrin,dichlorvos, bendiocarb, fenitrothion or chlorpyrifos. Insecticides suchas pyrethrin and pyrethroid can be effective as larvicides formosquitoes.

Various herbicides that may be employed, especially effective aquaticherbicides include Amitrole®, ammonium sulfamate, Bromacil®, coppersalts, dalapon, Dichlorbenil®, Diquat®, Diuron®, Endothall®, Fenac®,Picloram®, Prometon®, Silvex®, Simazine®, trichloroacetic acid, 2,4-D,2,4,5-T, Velpar®, TSMA, dicamba, endothall, silvex, prometon, chlorate,sodium metaborate, monuron, and various combinations thereof, such asthe two, three or four component combinations. Other insecticides,herbicides or fungicides that may be employed are set forth by Page &Thomson The Ouick Guide, Thomson publications 1987, Thomson,Agricultural Chemicals, Book I, Insecticides; Book II, Herbicides; BookIII, Fumigants, Growth Regulators, Repellants, 1985-87 revisions, all ofwhich are incorporated herein by reference.

Control of floating and submersed aquatic weeds is also of specialinterest. Bioactive agents included in the compositions and processesfor these applications include acrolein, aromatic solvents (xylene),copper sulfate and other water soluble copper salts or compounds,dalapon, dichlorbenil, 2,4-D, diquat, endothall, glyphosate, simazine,and fluridone, and combinations thereof, such as the two, three or fourcomponent combinations.

The aquatic organisms that are of special interest and which can betreated by the compositions of the present invention, and in accord withthe methods of the present invention include disease carrying or bitingor non-biting. insects (e.g., mosquitoes, sand flies, black flies,midges), or other animals (e.g., fish, barnacles, snails) or aquatic andwetland plants, and especially parasitic animals (e.g., nematodes,mollusks, protozoans, and bacteria) or floating or submersed nuisanceweeds e.g., algae, duckweed, hydrilla, water hyacinth, chara,watermilfoil, cattail bass weed, burreed, coontail, and the variouspondweeds including bushy, curly-leaf, flat stem, floating-leaf, horned,and sago; water star grass, arrowhead, bladderwort, bulrush, hornwort,creeping water primrose, pickerelweed, spatterdock, cow lily, yellowwater lily, waterweed, water chestnut, water smart weed, white waterlily, naiad, watershield, elodea, hydrollia, alligatorweed, cattails,giant cutgrass, guineagrass, knotgrass, maidencane, paragrass,phragmites, spatterdock, and torpedograss.

It should be noted that any bioactive agent, and combinations thereof,such as the two, three or four component combinations, designed forpromoting, enhancing (e.g., nutrients, flavorants, medicaments) orterminating (e.g., pesticides, or herbicides) the life of aquatic orterrestrial organisms can be utilized in the compositions of matter,depending on the desired end result. Specific controlled releasecompositions will be designed to deliver the desired bioactive agent(s)in the targeted portion(s) of the water column of an aquatic habitat orto a specific targeted area of a land mass.

These bioactive materials, and organisms are further described by Levyin U.S. Pat. No. 4,818,534, columns 12-14; U.S. Pat. No. 4,983,389,columns 11-13; U.S. Pat. No. 4,985,251, columns 4, 10, and 12-14; allthe foregoing being incorporated herein by reference.

The coatings that may be employed according to the present invention areselected so as to act as materials that will regulate the controlledrelease rate and release profile of bioactive agents over a period oftime in an aqueous or non-aqueous medium, and accordingly have to bewater soluble or partially water soluble and biodegradable, or insolublein water, and biodegradable or erodible, and/or film-forming on contactwith water. Coatings may also protect bioactive agents fromphotodegradation or biodegradation. The coatings have a specific gravityequal to or greater than one or less than one, and are liquids orsolids, and generally consists of either fatty alcohols or acids, orfatty alcohol esters of citric, glycolic, trimelletic or phthalic acid,or any mono, di- or tricarboxylic acid having from one to about 18carbon atoms, whether saturated or unsaturated, aliphatic or cyclic, andwhich are well known in the art. The fatty alcohols in this regardcomprise those alcohols having from about 5 to about 18 carbon atoms,and include the saturated as well as unsaturated aliphatic fattyalcohols. The aliphatic acids or alcohols include the straight chain andbranched chain isomers.

The coatings having a specific gravity less than one may comprisen-butyryl-tri-n-hexyl citrate, monostearyl citrate, stearyl alcohol,cetyl alcohol, myristyl alcohol, octadecanoic acid, glyceryl stearate,or waxes whereas the coatings having a specific gravity greater than onemay comprise, triethyl, acetyltriethyl citrate, tri-n-butyl citrate,acetyltri-n-butyl citrate, acetyltri-n-hexyl citrate,tri-n-hexyltrimellitate, dicyclohexyl phthalate, diethyl phthalate,butyl phthalyl butyl glycolate, dimethyl isophthalate, or water-solublefilms of polyvinyl alcohol, polyethylene oxide, methyl cellulose, andhydroxypropyl methyl cellulose, and combinations thereof, such as thetwo, three or four component combinations. It should be noted thatwater-soluble films can act in a coating/carrier capacity in certaincompositions of matter. Two or more coatings can be combined to modifyor enhance the controlled release rate or release profile of one or morebioactive agents in a composition.

One aspect of the invention comprises applying the coating with thebioactive material to the carrier and/or any continuous or discontinuoussurface such as walls, foundations, screening, fibers, fabrics, clothingand the like. Thus in terrestrial applications, the composition of theinvention comprises at a minimum, the coating material and the bioactiveagent that can be appplied to any substrtate, including the carrier,where the carrier comprises an optional component.

Especially suitable coatings comprise high molecular weight organicplasticizer coatings and include by way of example the followingmaterials:

Acetates

Glycerol diacetate

Glycerol monoacetate

Glycerol triacetate

Cumylphenyl Acetate

triethylene glycol diacetate

Adipic Acid Derivatives

Dibutoxyethoxyethyl adipate

Dicapryl adipate

Di(2-ethylhexyl) adipate

Di(n-heptyl,n-nonyl)adipate

Diisobutyl adipate

Diisodecyl adipate

Diisononyl adipate

n-Octyl, n-decyl adipate

Dioctyl adipate

Di(tridecyl)adipate

Alkyl alkylether diester adipate

Dibutoxyethoxyethyl adipate

Dibutoxyethyl adipate

Dimethyl adipate

n-Octyl,n-decyl adipate

Polyester adipate

Poly(propylene glycol adipate)diol cocoate

Poly(neopentyl glycol adipate)diol

poly(diethylene glycol adipate)diol

Azelaic Acid Derivatives

Dibutyl azelate

Di-(2-ethylhexyl) azelate

Diisodecyl azelate

Diisooctyl azelate

Dimethyl azelate

Di-n-hexyl azelate

Dibenzyl azelate

Dibutoxyethyl azelate

Diisobutyl azelate

Dioctyl azelate

Benzoic Acid Derivatives

Benzyl Benzoate

Diethylene gycol dibenzoate

Dipropylene glycol dibenzoate

Glycerol dibenzoate

Polyethylene glycol 200 dibenzoate

Propylene glycol dibenzoate

Tripropylene glycol dibenzoate

Tetrapropylene glycol dibenzoate

Octadecy benzoate

Glucose benzoate

2,2,4,-trimethyl-1,3-propanediol dibenzoate

Pentaerythritol tetrabenzoate

1,6-Cyclohexane dimethanol dibenzoate

Caprylic/Caproic Acid Derivatives

N,N-Dimethyl caprylamide capramide

Propylene glycol dicarprylate/caprate

Tetraethylene glycol dicaprylate/caprate

Triethylene glycol caprylate/caprate

Trimethylolethane tri caprylate/caprate

Trimethylopropane tri caprylate/caprate

Pentaerythritol tetra caprylate/caprate

Citric Acid Derivatives

Acetyltri-n-butyl citrate

Acetyl triethyl citrate

Acetyltri-n-(octyl/decyl) citrate

Acetyl-n-trihexyl citrate

n-Butyltri-n-hexyl citrate

Stearyl Citrate

Monostearyl citrate

Tri-n-butyl citrate

Triethyl citrate

Triethyl citrate polyethylene glycol

Trimethyl citrate

Coco Acid Derivatives

Tetraethylene glycol dicocoate

Dimer Acid Derivatives

Bis-(2-hydroxyethyl) dimerates

Epoxy Derivatives

Epoxidized linseed oil

Epoxidized soybean oil

2-Ethylhexyl epoxytallate

Epoxidized octyl tallate

Epoxidized glycol dioleate

Fumaric Acid Derivatives

Dibutyl fumarate

Glutarates

Long chain alkyl alkylether diester

Dialkyl diether glutarate

Dibutoxyethoxyethyl glutarate

Dibutoxyethyl glutarate

Diisodecyl glutarate

Polyester glutarate

Glycolic Acid Derivatives

n-butyl-phthaiyl-n-butyl glycolate

Heptanoic Acid Derivatives

Tetraethylene glycol diheptanoate

Triethylene glycol diheptanoate

Tetraethylene glycol diheptanoate

Trimethylopropane triheptanoate

Isobutyrate Derivatives

2,2,4-Trimethyl-1,3-pentanedial, diisobutyrate

Isophthalic Acid Derivatives

Dimethyl isophthalate

Diphenyl isophthalate

Lauric Acid Derivatives

Dioctyl dodecanedioate

Diisooctyl dodecanedioate

Isopropyl laurate

Methyl laurate

Polyethylene glycol 400 dilaurate

Polyethylene glycol 200 monolaurate

Polyethylene glycol 400 monolaurate

Polyethylene glycol 600 monolaurate

Polyoxyethylene laurate

Polyoxyethylene laurate, self emulsifying

Linoleic Acid Derivatives

Methyl linoleate, 50%

Maleic Acid Derivatives

Di(2-ethylhexyl) maleate

Di-n-butyl maleate

Mellitic Acid Derivatives

Tricapryl trimellitate

tri-n-hexyl-trimellitate

Triisodecyl trimellitate

Triisononyl trimellitate

Tri-(n-octyl, n-decyl) trimellitate

Trioctyl trimellitate

Nyristic Acid Derivatives

Isproply myristate

Octanoic Acid Derivatives

Propylene glycol di-2-ethylhexonoate

Trimethylolpropane trioleate

Pentaerythritol tetraoleate

Polyethylene glycol 400 di-2-ethylhexoate

Tetrathylene glycol di-2-ethylhexoate

Triethylene glycol di-2-ethylhexoate

Oleic Acid Derivatives

Butyl oleate

Glycerol monooleate

Glycerol trioleate

Methyl oleate

n-Propyl oleate

Tetrahydrofurfuryl oleate

Alkyl oleate

Butoxyethyl oleate

Glycerol oleate

Polyethylene glycol 400 dioleate

N,N-Dimethyl oleamide

Polyethylene glycol 200 monooleate

Polyethylene glycol 600 monooleate

Trimethylolpropane trioleate

Pentaerythritol tetraoleate

Palmitic Acid Derivatives

Isopropyl palmitate

Methyl palmitate

Paraffin Derivatives

Chloroparaffin, 41% Cl

Chloroparaffin, 50% Cl

Chloroparaffin, 60% Cl

Chloroparaffin, 70% Cl

Pelargonic Acid Derivatives

Triethylene glycol dipeargonate

Phosphoric Acid Derivatives

2-Ethylhexyl diphenyl phosphate

Isodecyl diphenyl phosphate

t-Butylphenyl diphenyl phosphate

Tri-butoxyethyl phosphate

Tributyl phosphate

Tricresyl phosphate

Triphenyl phosphate

Phthalic Acid Derivatives

Alkyl (C₁/C₉) benzyl phthalate

Butyl benzyl phthalate

Butyl octyl phthalate

Di-n-butyl phthalate

Dibutoxyethoxyethyl phthalate

Dicapryl phthalate

Dicyclohexyl phthlate

Di-(2-ethylhexyl) phthalate

Diethyl phthalate

Diheptyl, nonyl, undecyl phthalate

Dihexyl phthalate

Diisobutyl phthalate

Diisodecyl phthalate

Diisoheptyl phthalate

Diisononyl phthalate

Diisooctyl phthalate

Dimethyl phthalate

Dinonyl phthalate

Dinonyl, undecyl phthalate

Ditridecyl phthalate

Diundecyl phthalate

Undecyl dodecyl phthalate

Ricinoleic Acid Derivatives

Butyl ricinoleate

Glyceryl tri-(acetyl) ricinoleate

Methyl acetyl ricinoleate

Methyl ricinoleate

n-ButyL acetyl ricinoleate

Propylene glycol ricinoleate

Sebacic Acid Derivatives

Dibutyl sebacate

Dibutoxyethoxyethyl sebacate

Dibutoxyethyl sebacate

Di-(2-ethylhexyl) sebacate

Dioctyl sebacate

Dimethyl sebacate

Polyester sebacate

Stearic Acid Derivatives

Ethylene glycol monostearate

2-Ethylhexyl stearate

Tridecyl stearate

Glycerol monostearate

Isopropyl isostearate

Methyl stearate

n-Butyl stearate

Isobutyl stearate

Proylene glycol monostearate

Stearic acid ester amide

Succinic Acid Derivative

Diethyl succinate

Sulfonic Acid Derivatives

N-n-Butylbenzenesulfonamide

N-Ethyl o,p-toluenesulfonamide

o,p-Toluenesulfonamide

Mineral oil/sulfonate blend

Mineral oil/sulfonate ester blend

Naphthenic oil/sulfonate ester blend

Tallates

Epoxidized tallate

Isooctyl tallate

Octyl tallate

Toluic Acid Derivatives

N-N-Diethyl m-toluamide

Flame-retardant Plasticizers

SANTICIZER® 2148 alkyl aryl phosphate-(liquid)

SANTICIZER® 148 alkyl aryl phosphate-(liquid)

SANTICIZER® 141 alkyl aryl phosphate-(liquid)

SANTICIZER® 143 modified triaryl phosphate-(liquid)

Alkylene Glycols and Esters

methoxy polyethylene glycol, poyethylene glycol and propylene glycolpolymers and copolymers with one another, about 190 to about 19,000 M.W.

Miscellaneous

Hydrogenated Terphenyl HB-40®

Nipol® Liquid Nitrile Elastomers

JAYFLEX® 210 Plasticizer

(naphthenic hydrocarbon)

JAYFLEX® 215 Plasticizer

(aliphatic hydrocarbon)

STAN-FLUX™

Aromatic Process Oils

STAN-LUBE™

Paraffinic Process Oils

2-Hydroxyethyl ethylene Urea

Dibutoxyethoxyethyl formal

Polyol Esters made by reacting short to long chain carboxylic (C₅-C₁₈)acids with neopentyl polyols such as neopentyl glycol trimethyloethane,trimethylopropane, and pentaerythritol

LEXOLUBE®—Isopropyl Esters where isopropyl alcohol is reacted withstraight chain fatty acids ranging from lauric (C-12) to stearic (C-18)acid to produce an highly esterified product

Polyoxyethylene Esters made by reacting medium to long chain(C₉-C₁₈)carboxylic acids with tetraethylene glycol

LEXOLUBE®—Complex esters (the Z-series) ranging from a viscosity (40°C.) of 200 to 1000 centistokes based upon adipic acid backbone chemistry

LEXOLUBE® derived from the condensation of isobutanol with a triplepressed grade of stearic acid

LEXOLUBE® derived from the esterification of myristic acid(tetradecanoic acid) with isopropanol (2-propanol)

LEXOLUBE® Z-100 derived from the co-condensation of poly(propyleneglycol adipate)diol with coconut fatty acid

LEXOLUBE® T-110 derived from the condensation of 2-ethylhexanol with atriple pressed grade of stearic acid

LEXOLUBE® 2J-237 derived from the condensation of tetraethylene (TEG)glycol with a whole cut grade of coconut fatty acid

LEXOLUBE® 2N-237 derived from the condensation of tetraethylene glycol(TEG) with a carboxylic acid blend consisting primarily of octanoic acidand decanoic acid

LEXOLUBE® 2N-237 derived from the condensation of tetraethylene glycol(TEG) with a carboxylic acid blend consisting primarily of octanoic acidand decanoic acid.

The range of molecular weights for the high molecular weight organicplasticizer coating component will range from the approximate molecularweight of the lowest molecular weight compound listed herein toapproximately the highest molecular weight of the compounds listedabove.

These high molecular weight organic plasticizer compounds also includeepoxidized vegetable oils, naphthenic hydrocarbons and long chainaliphatic hydrocarbons or paraffin type oils as well as chlorinatedparaffins all of which are well known in the art and noted above.

Ester coating compounds are especially preferred, particularly theesters listed herein.

The foregoing high molecular weight organic plasticizer compoundsespecially comprise organic esters based on the reaction of organicacids and organic alcohols or inorganic acids and organic alcohols wherethe inorganic acids comprise phosphorous acids and sulfur acids known inthe art.

The organic acid esters are especially preferred, and particularlyorganic acids having from 1 to about 4 carboxyl groups, up to about 18carbon atoms and can be saturated or unsaturated straight chain orcyclic structures including polyunsaturated compounds such as aromaticcompounds and aliphatic or alicyclic compounds.

The preferred organic alcohols have from 1 to about 4 hydroxy groups, upto about 18 carbon atoms and can be saturated or unsaturated straightchain or cyclic structures including polyunsaturated compounds such asaromatic compounds and aliphatic or alicyclic compounds.

The coatings based on the high molecular weight organic plasticizershave a release profile controlled by solubility, hydrolysis,biodegradation, erosion, and/or other types of degradation of the esters(when employed) as well as other additives.

In addition to being applicable to treating organisms in columns ofwater and in surface or sub-surface areas of terrestrial habitats in themanner set forth herein, these compositions of matter comprising acontrolled delivery system based on these high molecular weight organicplasticizers and other coating materials find use as seed coatings,medicament coatings, e.g., trans dermal patches or implants oradmixtures with medicaments and the like.

In one application, in order to minimize allergic reactions of hoovedanimals to the application of various bioactive materials as definedherein, e.g. a repellant, the compositions find use in coating thehooves of hooved animals where the bioactive material vaporizes andmoves upwards towards the animal, and/or remains in or on the ground. Insome instances, where the bioactive material or combination of bioactivematerials include those that are not vaporizable, the application of thecomposition of matter to the feet of the animal will provide a way ofapplying the composition to the terrestrial environment of the animaland can find use for the treatment of marshy or swamp areas, e.g., forimmature mosquitoes, as well as dry land areas where the animal movesabout.

In addition, in those applications that do not involve treating a columnof water, the compositions of the invention find use in coating fibers,fiber glass, walls, baseboards, building materials, (includingwallboards, e.g. gypsum, press board, concrete blocks, cement walls andthe like) to make the composition of the invention available fortreating terrestrial organisms.

The coatings, bioactive agents and carriers may also be combined withwater soluble or insoluble, hydrophilic or hydrophobic, biodegradable orerodible, cross-linked or non-crossed-linked, binder materials such assulfonated polystyrene homopolymers, sulfonated styrene maleic anhydridepolymers, sulfonated vinyl toluene maleic anhydride polymers, vinylpyrrolidine polymers or copolymers, poly(isobutylene-co-disodiummaleate) copolymers, acrylamide polymers or copolymers,acrylonitrile-starch graft polymers or copolymers, carboxymethylcellulose polymers or copolymers, acrylate polymers or copolymerspoly(vinyl alcohol) polymers or copolymers, poly(ethylene oxide)polymers or copolymers, acrylic acid or acrylic ester homopolymers orcopolymers, modified food starch (CAPSULE® and N-LOCK®), natural orsynthetic gums, poly (ethylene glycol), clays, gypsum, plaster of Paris,wax, paper, and especially paper as described herein including withoutlimitation, BIODAC®, cellulose, latex, methyl vinyl ether maleic acidester copolymers, and various starches and modified starches asdescribed by Davidson Book Of Water-Soluble Gums And Resins, 1980,chapter 22, BP.22-1 to 22-79 which is by reference, and combinationsthereof such as the two, three or four component combinations toagglomerate the controlled release compositions into larger units suchas granules, pellets, briquets, or extrusions.

The foregoing polymers or copolymers which comprise superabsorbentpolymers are especially useful in forming agglomerates of thecompositions of the present invention. The various processes are knownfor forming these agglomerates some of which are described in Ferro-TechGeneral Catalog, Form 317, 8-1-83, revised 12-85 which is incorporatedherein by reference, and is published by the Ferro-Tech® Corporation,467 Eureka Road, Wyandotte, Mich. 48192, which is incorporated herein byreference.

The controlled release compositions may also be combined with otherformulating materials or ingredients or components wherein suchcomponents are diluents, adjuvants, dyes, alcohols, acetone, ketones,oils, surfactants, water, emulsifiers, film-forming agents,compatibility agents, wetting agents, salt, natural or syntheticpolymers, hydrocolloids, buoyancy modifiers, ultraviolet absorbers,photo-protecting agents, suspending agents, elastomers, penetrants,deflocculating agents, dispersing agents, stabilizing agents,antifoaming agents, sticking agents, solvents, co-solvents, catalysts,or synergists, and the like, and combinations thereof, such as the two,three or four component combinations.

Components of the present invention can be homogeneously orheterogeneously combined into the desired controlled deliverycompositions or complexes for treating a population of aquatic organismsin an aquatic or preaquatic or terristrial environment by admixing theindividual solid, and/or liquid formulation components in aconcentration, and order to effectively impregnate or encapsulate thecarrier(s) with the desired concentration of coating agent(s) andbioactive agent(s).

Admixing with one or more optional binders, and/or formulation materialscan be utilized to agglomerate the composition(s) into larger units,and/or to achieve optimum controlled release performance. Formulationcomponents can also be fabricated into solid controlled deliverycompositions by coupling aqueous admixing procedures with solvent basedadmixing procedures.

To further modify the controlled delivery rate and release profile ofcompositions of matter of the present invention, liquid, powdered,granular, film or agglomerated compositions can be placed into flexibleor rigid polyvinyl alcohols, polyethylene oxide, and/or hydroxypropylmethyl cellulose film containers (e.g., pouches, packets, capsules,extrusions) of varying water solubilities. In addition, compositions canbe optionally placed into various shaped (e.g., spherical, cylindrical,etc.) dispensers (e.g., plastic, glass, metal, etc.) having a specificgravity greater than or less than one, with one or more orifices (e.g.,holes, slots, etc.) in the wall(s) of the dispensing device to modifythe controlled release rate and release profile of the bioactive agentfrom the compositions of matter through the orifice(s) into a watercolumn. Pretreatment application of these dispensing devices is alsowithin the scope of the present. invention.

An example of a commercially available products that may be employed inthis regard comprise DISSOLVO™-POUCH which is a polyvinyl alcohol filmpouch. The various dimensionally stable solvable pouches are furtherdescribe by Miller in Pesticides Formulations and Application System;8th Vol., ASTM STP 980, D. A. Hovde et al., EDS. American Society forTesting and Materials, Phil. 1988, which is incorporated herein byreference.

The compositions of the present invention can be formulated totime-release one or more bioactive agents from the carrier to treat apopulation of organisms in specific areas of a water column of anaquatic environment or in specific surface or subsurface areas of aterrestrial environment according to zero-order, first-order, orsquare-root-of-time kinetics. In general, depending on the type,concentration, and number of coatings utilized on a composition, and theformulation procedures utilized in fabricating the compositions,controlled delivery of one or more bioactive agents from the carrier canbe fast, slow, delayed or pulsed. Controlled release formulations can beprepared wherein the materials for the preparation of such controlledrelease compositions are described by Wilkins, Controlled Delivery OfCrop-Protection Agents, 1990, Kydonieus, Controlled ReleaseTechnologies: Methods, Theory And Applications, Volumes 1 and 2, 1980;Barker Controlled Release Of Biologically Active Agents, 1987, Marrion,The Chemistry And Physics Of Coatings, 1994; Muller Carriers ForControlled Drug Delivery And Targeting, CRC press; Duncan and Seymour,Controlled Release Technology 1989; and Karsa and Stephenson,Encapsulation And Controlled Release 1993, all of which are incorporatedherein by reference.

Controlled release solid compositions utilized in the present inventionfor treating a population of one or more aquatic organisms consist ofabout 0.001% to about 50% by weight (w/w) of at least one coating agent,about 0.0001% to about 50% (w/w) of at least one bioactive agent, andabout 50% to about 99% (w/w) of at least one carrier; with or withoutabout 0.0001% to about 75% (w/w) of one or more binders, and/or one ormore formulating materials or about 0.1% to about 99.9% (w/w) of atleast one joint-function carrier/coating agent, about 0.001% to about90% (w/w) of at least one bioactive agent; with or without about 0.0001%to about 75% (w/w) of one or more binders, and/or one or moreformulating materials.

Controlled release solid compositions utilized in the present inventionfor specifically treating a population of one or more species ofmosquitoes in their aquatic stages, typically consist of about 1.0% toabout 25% (w/w) of at least one coating agent, about 0.01% to about 30%(w/w) of at least one bioactive agent, and about 70% to about 95% (w/w)of at least one carrier; with or without about 0.01% to about 60% (w/w)of one or more binders, and/or formulating materials or about 50% toabout 99% (w/w) of at least one joint-function carrier/coating, about0.1% to about 30% (w/w) of at least one bioactive agent; with or withoutabout 0.01% to about 60% (w/w) of one or more binders, and/orformulating materials. Solid compositions of the present invention canoptionally be suspended in water or oil for application as a liquidspray.

In the embodiment of the present invention comprising complexes fortreating a population of one or more aquatic organisms in a column ofwater, the complexes comprise at least one controlled delivery system,and especially from about one to about three controlled deliverysystems. Each controlled delivery system in turn comprises at least onecarrier, at least one bioactive agent as a component for treating apopulation of one or more aquatic organisms, and at least one coatingcomponent or at least one joint-function carrier/coating agent forregulating the controlled release rate and release profile of thebioactive agent in water with or without one or more binder componentsas an agglomeration aid or one or more additional formulation materials,which is intended to mean anywhere from one to about three of each ofthese components.

By properly selecting one or more of the various bioactive components,and/or other components, a composition of matter can be provided thatwill be effective to treat a population of one or more aquatic organismsor a plurality of aquatic organisms at either the surface, subsurface,the bottom or, the entire column of water.

Each one of these components is selected to sink or float so that thecomplex will permeate and remain in any planar or volumetric segment ofa water column for a period of time sufficient to treat a population ofone or more aquatic organisms.

It should be noted in this regard that even though silica has a specificgravity greater than one, a finely divided silica that has been surfacetreated with silicone, as noted herein, will float because of thehydrophobic properties imparted to it by the silicone coating.Accordingly, the hydrophobicity of the components in the composition ofmatter has to be taken into account when formulating the composition ofthe present invention by adjusting the type, and/or quantity of thehydrophobic component(s) employed.

Similarly, the density or the flotation properties of the othercomponents of the compositions of matter of the invention have to betaken into account, as well as the quantity of such components whenformulating the compositions of the invention so that it will bedelivered to the appropriate planar or volumetric segment of the columnof water that is to be treated according to the processes of theinvention. When this formulation method is employed, a controlleddelivery composition of matter can be prepared having a buoyancyselected to treat any part of a water column, or an entire water column.

Thus, a controlled delivery composition of matter can be prepared basedon a carrier that sinks, and a bioactive material and coating thatfloats, each being employed in amounts that can be readily determined,so that the bioactive material will be taken to the bottom of a watercolumn by the carrier, and upon exposure to water in the column, thecoating will be released, and carry the bioactive material to thesurface to treat any surface organisms or any organisms encountered inmoving toward the surface. An example of a controlled delivery systemlike this comprises sand coated with the optimum concentration of cetylalcohol in combination with a bioactive material that floats.

Similarly, a carrier can be selected that floats in combination with acoating that floats, and a bioactive material that sinks, where thetypes and quantities of each are experimentally determined so that thecomposition floats. Upon exposure to water, the coating will release thebioactive material which will move towards the bottom of the column, andtreat any aquatic organisms that are at the bottom or encountered inmoving toward the bottom of the column. An example of a controlleddelivery composition of matter that will function in this way comprisessilica that floats, i.e., hydrophobic finely divided silica coated witha silicone material, in combination with cetyl alcohol, and any knownbioactive material that sinks.

Another controlled delivery composition of matter can be prepared basedon a carrier and bioactive agent that sinks, and a coating that floatseach being employed in amounts that can readily be determined so thatthe bioactive material will be taken to the bottom of a water column bythe carrier, and upon exposure to the water the coating will bereleased, and initially carry the bioactive agent to the surface totreat any surface organisms encountered in moving toward the surface,and then after being maintained at the surface for some period of time,the bioactive agent will slowly move toward the bottom where it will beavailable to treat organisms on the downward movement through the watercolumn, and at the bottom of the water column. An example of acontrolled delivery system like this comprises sand coated with anoptimum concentration of cetyl alcohol in combination with a bioactiveagent that sinks.

Furthermore, compositions of matter of the invention comprising ajoint-function carrier/coating agent, and bioactive agent, such as asinking, and/or floating joint-function carrier/coating agent, or ajoint-function carrier/coating agent, an additional coating agent, and abioactive agent can be developed to distribute a bioactive agent todesired areas or volumes of a water column over time, or to one or moreterrestrial organisms over time. Especially suitable joint-functioncarrier/coating agents comprise polyvinyl alcohol, polyethylene oxide,hydroxypropyl methyl cellulose, cetyl alcohol or stearyl alcohol andvarious combinations thereof such as the two, three or four componentcombinations.

All compositions can be optionally combined with a binder to agglomeratethe composition into larger units such as granules, pellets, andbriquets, or an additional formulation ingredient. In addition, allcompositions can also be optionally dispensed in a water column enclosedwithin water soluble film containers, and/or dispensed from deviceshaving one or more orifices open.

From these descriptions, it is obvious that one or more floating, and/orsinking carriers, coatings, and bioactive agents with or without bindersor additional formulation ingredients car be combined in variouspermutations, and combinations into controlled release compositions thatare designated to target desired areas or volume segments of a watercolumn or an entire water column to treat a population of one or moreaquatic organisms.

It should be noted in this regard that the water column is defined as avolume of water underneath the surface of water of a specified area thatrequires treatment, the body of water including ponds, lakes, bays,wetlands, marshes, swamps, tidal basins, lagoons, sounds, creeks,streams, rivers, oceans, ditches, swales, sewage treatment controlleddelivery systems, potholes, tree holes, rock holes, bromeliads, tires,which is to say moving or stagnant water containing one or more targetorganisms. Thus, the treated column of water can be either moving orstationary, and have any water quality that can be utilized as a habitatfor the target organism(s).

By treating a column of water, as that term is employed herein, it isintended not only to provide the compositions of matter of the presentinvention to a column of water that is infested with aquatic organismsthat exist in the column, but also a column of water that has thepotential of being infested with aquatic organisms. Compositions ofmatter of the present invention are also provided for pretreatmentapplication to a dry habitat that has not yet flooded by rain, tides,and the like, to produce a defined water column where aquatic organismsare known to breed, i.e. a preflood area. Compositions of matter forpretreatment of an existing water column that is not yet infested withaquatic organisms or that are infested with organisms are also withinthe scope of the invention.

Compositions of matter are also provided, for treating terrestrialorganisms in a land mass. A land mass can include any natural orartificial surface or subsurface area of a iterrestrial environment.

The compositions of the present invention can be applied by ground oraerial techniques in any form such as liquids powders, granules,agglomerates, pellets, and briquets. These forms can be encapsulatedwithin water soluble or porous, or degradable pouches, capsules, filmsor sheets, which may comprise polyvinyl alcohol, polyethylene oxide,hydroxypropyl methyl cellulose, paper, or gelatin, and/or within deviceshaving one or more orifices in contact with the water column or landmass. The compositions of the present invention can also be applied aswater, and/or oil based formulations.

In the following examples powdered and agglomerated controlled deliverycompositions of matter are utilized as examples to illustrate thepresent invention, and were designed to target surface, subsurface, orboth surface, and subsurface areas of an aquatic habitat. Larvae ofAnopheles spp. mosquitoes were used as models to demonstrate theefficacy of surface active compositions, while larvae of Aedes spp. andCulex spp. mosquitoes were used to demonstrate subsurface efficacy.

Insecticidal bioactive agents admixed with a variety of carriers andcoatings or joint-function carrier/coatings, with or without binders orformulating materials, were commercial formulations of the bacteriaBacillus thuringiensis var. israelensis (B.t.i.) (Acrobe® TechnicalPowder, Acrobe® Biolarvicide or Vectobac® Technical Powder), the insectgrowth regulators methoprene (Dianex® Emulisifiable Concentrate),pyriproxyfen (Nylar® Technical or Emulsifiable Concentrate); a mixtureof Acrobe® TP, and Dianex® EC, the organophosphate temephos(Abater 4-E)or an experimental monmolecular surface film (POE(2) 2 mol ethoxylate ofisostearyl Alcohol). Additional insecticidal bioactive agents admixedwith a variety of coatings and carriers, with or without binders orformulation materials, that were not utilized in mosquito bioassays,were commercial formulations of the insect growth regulatorsdiflubenzuron (Dimilin® Wettable Powder) the bacteria Bacillussphaericus (ABG-6184), the fungus Lagenidium giganteum, and thepetroleum oil (GB-1111). Examples of liquid or solid coatings utilizedin the compositions of matter to regulate the controlled release rateand release profile of the bioactive agent(s) from the carrier wereesters of citrate (Citroflex®2, A-2, 4, A-4, A-6 or B-6), phthalate,glycolate, trimellitate (Morflex® 150, 190, or 560), cetyl alcohol,and/or polyvinyl alcohol films (MonoSolo® 7000 or 8000 series). Coatingsranged from water soluble to insoluble, and had specific gravities lessthan or greater than one. Solid carriers utilized in the compositions ofmatter as surface or subsurface-active bioactive agent delivery matriceswere hydrophobic (Sipernat®D17, and Aerosil®R972) or hydrophilic(Wesslon™, Wesslon™ 50, Sipernat®22S, and FK 500 LS) Degussa silicas,sand (Texblast®), cetyl alcohol (Sigma®) (specific gravity less thanone), and/or corn cob granules, BIODAC® granules and/or polyvinylalcohol films (MonoSol®7000 or 8000 series) (specific gravity greaterthan one). Polymeric binders utilized in the examples to agglomerate thepowdered compositions into larger units were soluble starch (Difco®),sulfonated polystyrene (Versa®TL-502), sulfonated vinylic copolymers(Narlex® D-82), acrylic copolymer (Carboset®514H), and acrylic polymer(Carbopol®ETD 2001 Resin). Additional formulation materials such aswater, soluble or insoluble alcohols (2-propanol, 2-ethyl hexanol, 2 molethoxylate of isostearyl alcohol) or ketones (acetone, methyl ethylketone) were also utilized as admixture components in selectedcompositions.

A series of bioassays were designed to demonstrate the short orlong-term mosquito-controlling effectiveness of a variety of powderedand agglomerated compositions that were formulated to time-release oneor more mosquitocidal bioactive agents in specific areas of a watercolumn or the entire water column. Composition transfer bioassays wereutilized to evaluate the controlled release duration of selectedpowdered, granular or agglomerated formulations. The efficacy ofpretreatment compositions was also evaluated. Powdered, granular oragglomerated compositions were evaluated at ca. 27° C. in 0.019 m² ½ galplastic containers containing 1000 ml of fresh water (purified byreverse osmosis filtration) or brackish (10% Instant Ocean®/distilledwater) water and ten 1st to 4th instar larvae of the Anopheles, Aedes,or Culex species. Bioassays were also conducted with mixed speciespopulations. Tests with each powdered, granular or agglomeratedcontrolled delivery composition were replicated three times.

The following examples are illustrative of the controlled deliveryfabrication protocols, types of powdered, granular, agglomerated orextruded controlled release compositions, and processes for treating apopulation of aquatic or terrestrial organisms in a column of water oron land.

EXAMPLE 1

The admixing protocol for the components utilized in the powderedcomposition (Code J) in this bioassay series against mosquito larvae wasas follows: 10 g cetyl alcohol (heated to 60° C.) and 5 g triethylcitrate (Citroflex®2) were each added separately to 300 g acetone in ½gal plastic beakers and mixed with a laboratory hand mixer (GE® Model420A) for ca. 5 minutes. 5 g of B.t.i. (Acrobe®TP) was then slowly addedto each coating formulation while mixing for an additional 5 minutes. 85g and 90 g hydrophobic silica (Sipernat®D17) were slowly added to thecetyl alcohol and triethyl citrate formulations of bacteria,respectively, while mixing for an additional 2½-3 hr to drive off theacetone and assure that the B.t.i. and each coating were uniformlyimpregnated on the silica carrier. Powdered compositions were placed ina low humidity room (27-38% RH; 76-79° F.) for an additional 4 hr toassure volatilization of the acetone. Each powdered formulation wasstored in Zip-lock™ bags or glass bottles. Sub samples of each of thetwo formulations were admixed at a 1:1 ratio for an additional 5 minutesto achieve the powdered composition utilized for testing.

Results of short-term bioassays against Anopheles, Aedes, and Culexspecies in fresh or brackish water with a powdered controlled deliverycomposition comprising a 1:1 blend of an acetone-base (300 g) admixtureformulation (w/w) of 5 g of B.t.i. (specific gravity greater thanone/insoluble in water) labeled Acrobe®TP (3864 ITU/mg), 10 g cetylalcohol (specific gravity less than one/insoluble in water), and 85 ghydrophobic silica (Sipernat®D17) and another acetone-base (300 g)admixture formulation (w/w) of 5 g Acrobe®TP, 5 g triethyl citrate(Citroflex®2; specific gravity greater than one/water soluble), and 90 gSipernat®D17 indicated that the multiply coated/,encapsulated B.t.i.could be released from the hydrophobic silica carrier at varyingintervals/rates and provide effective control of both surface andsubsurface feeding mosquito larvae at extrapolated application rates ofca. 2.5 lb/surface acre of water (Table 1). The efficacy of thecomposition against the Anopheles species indicated that Acrobe®TP canbe maintained at the surface feeding area of an aquatic habitat for asufficient period of time to effectively allow the Anopheles larvae toingest lethal concentrations of toxic crystals of B.t.i. Efficacyagainst Aedes and Culex species suggested that the dense B.t.i. wasslowly released from the surface-active carrier/coating formulationbelow the surface of the water through the water column where the toxiccrystals were accessible to the subsurface and bottom feeding species.In general, the powdered controlled delivery composition was effectivein releasing sufficient concentrations of B.t.i. over a 1 to 5 dayposttreatment period to produce 100% control of surface or subsurfacefeeding mosquito larvae in fresh or brackish water. Controlled releaseof B.t.i. from the silica carrier to surface and/or subsurface areas ofa water column was a function of the type and concentration of coatingagents. The initial point of B.t.i. release and distribution at thewater interface was a function of the hydrophobic nature of the carrier.

TABLE 1 (Example 1). Coating-Regulated Delivery of Acrobe ® TP from aHydrophobic Silica Carrier* % Control of Larvae at Indicated Post-Mosquito Larval Water treatment Time Period (Days)** Species InstarQuality 1 2 3 4 5 Surface Feeders (Anopheles spp.) An. albimanus 2ndFresh 100.0 — — — — An. albimanus 3rd Fresh 83.3 90.0 100.0 — — An.albimanus 4th Fresh 23.3 60.0 80.0 100.0 — An. albimanus 2nd Brackish90.0 100.0 — — — An. albimanus 3rd Brackish 83.3 96.7 100.0 — — An.albimanus 4th Brackish 53.3 76.7 96.7 100.0 — An. quadrimaculatus 2ndFresh 100.0 — — — — An. quadrimaculatus 3rd Fresh 70.0 100.0 — — — An.quadrimaculatus 4th Fresh 50.0 50.0 53.3 96.7 100.0 Subsurface Feeders(Aedes and Culex spp.) Ae. aegypti 1st Fresh 100.0 — — — — Ae. aegypti3rd Fresh 53.3 90.0 100.0 — — Ae. taeniorhynchus 3rd Brackish 90.0 93.396.7 100.0 — Cx. quinquefasciatus 3rd Fresh 26.7 43.3 83.3 100.0 — *5%Acrobe ® TP (w/w) utilized in the controlled release composition. Cetylalcohol and triethyl citrate utilized as B.t.i. release-rate regulators(formulation ratio of 1 part cetyl alcohol/B.t.i.. to 1 part triethylcitrate/B.t.i.). **B.t.i. compositions applied as a powder at ca. 2.5lb/acre.

EXAMPLE 2

Another series of bioassays with other types of powdered controlledrelease compositions were conducted against larvae of Anopheles, Aedes,and mixed populations of Anopheles and Culex species in fresh andbrackish water. In formulating these compositions of matter, B.t.i.(Acrobe®TP) was admixed with other types of hydrophobic (Aerosil®R972)and/or hydrophilic (FK 500 LS) silica, hydrophobic wood “pin chips” orsaw dust (Sea Sweep®), or sand (Texblast®) carriers and cetyl alcoholand/or triethyl citrate (Citroflex® 2) coating agents into powderedcontrolled delivery compositions that had an affinity for targetingselected areas of an aquatic habitat (Table 2).

Results of a series of short-term bioassays with these powderedcontrolled release compositions are presented in Table 3. The dataindicated that the type(s) of powdered carrier(s) (e.g., hydrophobicand/or hydrophilic) and the type(s) and concentration ofcoating/encapsulation agent(s) e.g., specific gravity greater thanand/or less than one/water soluble and/or insoluble) utilized in apowdered composition would dictate the orientation of delivery in awater column and the rate of release of larvicidal bacteria. Allpowdered compositions provided 100% control of larvae in fresh orbrackish water. In general, results indicated that specific carriers andcoatings could be combined with B.t.i. in a manner to selectively targetsubsurface/bottom feeding mosquito larvae or mixed populations ofsurface and subsurface/bottom feeding mosquito larvae. The type ofcarrier was observed to initially orient the bioactive agent (i.e.,B.t.i.) in a surface or subsurface plane of the water column while thetype of coating agents would dictate controlled release persistence,rate, direction, and/or a change in the initially observed surface orsubsurface release plane of B.t.i.

TABLE 2 (Example 2). Formulation Components in Powdered ControlledDelivery Compositions* Composition No. Concentration of Admixtures inPowdered Compositions 1 5 g B.t.i. (Acrobe ® TP) + 5 g cetyl alcohol + 5g triethyl citrate (Citroflex ® 2) + 42.5 g hydrophobic silica(Aerosil ® R972) + 42.5 g hydrophilic silica (FK 500 LS) 2 5 g B.t.i.(Acrobe ® TP) + 10 g cetyl alcohol + 85 g hydrophilic silica (FK 500 LS)3 10 g B.t.i. (Acrobe ® TP) + 10 g triethyl citrate (Citroflex ® 2) +180 g hydrophobic “pin chips” (Sea Sweep ® ) 4 5 g B.t.i. (Acrobe ®TP) + 20 g cetyl alcohol + 75 g sand (Texblast ® ) *Cetyl alcohol(heated to 60° C.) and/or triethyl citrate was added to 300 g acetoneand mixed for 5 minutes with a GE ® Model 420A hand mixer in a ½ galplastic beaker. B.t.i. was slowly added to solvent-base formulation ofcoating(s) while mixing for an additional 5 minutes. Hydrophobic and/orhydrophilic silica or sand was ad-mixed with the other components whilemixing was continued for ca. 3 hr to drive off the acetone and assure ahomogeneous dry mixture # of all the components. Hydrophobic “pin chips”were ground with a Micro-Mill ® into a fine powder. Tri-ethyl citratewas added to a stainless steel bowl containing 800 g acetone and mixedfor ca. 5 minutes with a KitchenAid ® KSM 90 (speed #6) hand mixer.B.t.i. was added slowly and mixing was continued for ca. 5 minutes.Ground “pin chips” were slowly added to the mixture while blending wascontinued on speed #2 for ca. 4 hr until the powdered formulation wasdry. All powdered compositions were placed in a low-humidity room (ca.27-38% RH) for ca. 3 hr to assure volatilization of the solvent.Powdered compositions were stored in zip-lock bags or glass bottles.

TABLE 3 (Example 2). Coating-Regulated Delivery of Acrobe ® TP FromSeveral Types of Hydrophobic and Hydrophilic Carriers.* % Control ofLarvae at Mosquito Larval Water Composition Indicated Posttreatment TimePeriod (Days)** Species Instar(s) Quality No. 1 2 3 4 5 6 7 SubsurfaceFeeders (Aedes and Culex spp.) Ae. aegypti 2nd Fresh 1 76.7 90.0 96.7100.0 — — — Ae. aegypti 3rd Fresh 2 93.3 96.7 100.0 — — — — Ae.taeniorhynchus 3rd Brackish 1 90.0 100.0 — — — — — Ae. taeniorhynchus3rd Brackish 2 63.3 90.0 100.0 — — — — Ae. taeniorhynchus 3rd Brackish 340.0 83.3 96.7 96.7 100.0 — — Cx. quinquefasciatus 3rd Fresh 1 63.3 83.396.7 100.0 — — — Cx. quinquefasciatus 3rd Fresh 3 93.3 100.0 — — — — —Cx. quinquefasciatus 4th Fresh 1 100.0 — — — — — — Cx. quinquefasciatus4th Fresh 2 100.0 — — — — — — Subsurface/Surface Feeders (Culex andAnopheles spp.)*** Cx. quinquefasciatus/ 3rd/2nd Fresh 2 83.3 93.3 93.396.7 100.0 — — An. albimanus Cx. quinquefasciatus/ 3rd/2nd Fresh 4 50.063.3 66.7 90.0 90.0 93.3 100.0 An. albimanus *5% Acrobe ® TP utilized inall controlled release compositions. Cetyl alcohol and/or triethylcitrate utilized as B.t.i. release-rate regulators. **B.t.i.compositions applied as a powder at ca. 2.5 lb/acre. ***Mixed Culex andAnopheles larvae (1:1).

EXAMPLE 3

Powdered admixtures of B.t.i. (Acrobe®TP), a hydrophobic silica(Sipernat®D17) carrier, a cetyl alcohol coating, and a soluble starch,sulfonated polystyrene (Versa®TL-502) or sulfonated vinylic(Narlex®D-82) polymeric binder were also agglomerated by hand into aseries of controlled delivery briquets (Table 4). Small cubettes (ca.3.5×3.5×4.5 mm) were sectioned from each type of B.t.i. briquet andutilized in a series short-term bioassays against 2nd instar larvae ofAnopheles and Culex species in fresh and brackish water. One cubette perbioassay test chamber (i.e., plastic ½ gal beakers) was equivalent to anextrapolated application rate of ca. 5 lb/surface acre of water.

Evaluation of 3 types of Acrobe®TP cubettes against Anopheles and Culexlarvae indicated that the rate of control was a function of thecoating-regulated release of B.t.i. from the encapsulated silica and therate of binder-regulated dissociation of the powdered components fromthe agglomerated matrices in fresh or brackish water (Table 5).Observations indicated that the initial orientation of the Narlex®,soluble starch, and Versa® cubettes on introduction to water was sinks,sinks, and floats, respectively. Dissociation of Narlex®D and Versa®cubettes into smaller powder-like components occurred in ca. 5 minutesafter introduction into the fresh or brackish water, while solublestarch cubettes dissociated into several small subagglomerated units inabout 24 hr after introduction to fresh or brackish water. The smallersubagglomerated units were observed to dissociate into still smallerpowder-like components over a several day period. The hydrophobic silicacarrier coated with the insoluble, low specific gravity cetyl alcoholand B.t.i. was observed to float upon being released from the initialsurface or subsurface orientation of the cubette in the aquatic habitat.The series of agglomerated B.t.i. compositions produced 100% control oflarvae within-1 to 9 days posttreatment.

TABLE 4 (Example 3). Formulation Components in Allomerated ControlledDelivery Compositions* Composition Concentration Code of Admixtures inAgglomerated Compositions A 5 g 5 g B.t.i. (Acrobe ® TP) + 10 g cetylalcohol + 85 g hydrophobic silica (Sipernat ® D17) + 5 g sulfonatedpoly- styrene polymer (Versa ® TL-502) B 5 g 5 g B.t.i. (Acrobe ® TP) +10 g cetyl alcohol + 85 g hydrophobic silica (Sipernat ® D17) + 5 gsulfonated vinylic copolymer (Narlex ® D-82) C 5 g 5 g B.t.i. (Acrobe ®TP) + 10 g cetyl alcohol + 85 g hydrophobic silica (Sipernat ® D17) + 5g soluble starch *Cetyl alcohol (heated to 60° C.) was added to 300 gacetone and mixed for ca. 5 minutes with a GE ® Model 420A hand mixer ina ½ gal plastic beaker. B.t.i. was slowly added into the solven-baseformulation of coating while mixing for an additional 5 minutes.Hydro-phobic silica was mixed with the other components while mixing wascontinued for ca. 3 hr to drive off the acetone and assure a homogeneousdry mixture of all components. The powdered composition # was placed ina low humidity room (ca. 27-38% RH) for ca. 4 hr to assurevolatilization of solvent. A ratio of one part of this powdered 3-partbioactive agent/coating/carrier formulation was mixed with one partbinder (sulfonated polystyrene polymer, sulfonated vinylic copolymer orsoluble starch) for ca. 5 minutes. The 1:1 composition was then handcompacted into 25 × 20 × 5 mm vinyl specimen molds (Cryomold ® ) andplaced in a high humidity curing room (ca. 80% # RH and 80° F.) for ca.96 hr. Molds containing each compositon were then transferred to adrying room (ca. 27-38% RH, 76-79° F.) for an additional 96 hr. The drysolidified briquet compositions in each mold were stored in plasticzip-lock bags. Subsections of each briquet (i.e., ca. 3.5 × 3.5 × 4.5 mmcubettes) were utilized in the bioassays. One cubette (ca. 0.01 g) wasutilized against mosquito larvae in each bioassay test chamber (3replications/agglomerated # composition).

TABLE 5 (Example 3). Coating-Regulated Delivery of Acrobe ® TP fromAgglomerated Compositions* % Control of 2nd Instar Mosquito WaterComposition Larvae at Indicated Posttreatment Time Period (Days)**Species Quality Code 1 2 3 4 5 6 7 8 9 Surface Feeders (Anopheles spp.)An. albimanus Fresh A 93.3 100.0 — — — — — — — An. albimanus Fresh B100.0 — — — — — — — — An. albimanus Brackish A 90.0 100.0 — — — — — — —An. albimanus Brackish B 90.0 100.0 — — — — — — — An. albimunus BrackishC 16.7 33.3 33.3 43.3 86.7 96.7 100.0 — — An. quadrimaculatus Fresh A93.3 100.0 — — — — — — — An. quadrimaculatus Fresh B 96.7 100.0 — — — —— — — Subsurface Feeders (Culex spp.) Cx. quinquefasciatus Fresh A 100.0— — — — — — — — Cx. quinquefasciatus Fresh B 93.3 100.0 — — — — — — —Cx. quinquefasciatus Fresh C 23.3 43.3 63.3 70.0 83.3 86.7 90.0 96.7100.0 *5% Acrobe ® TP (w/w) utilized in each agglomerated controlledrelease B.t.i. composition. Compositions contained B.t.i., a cetylalcohol coating, a hydrophobic silica carrier, and a sulfonatedpolystyrene polymer, sulfonated vinylic copolymer, or soluble starchbinder (formulation ratio of 1 part bioactive agent/coating/carrier to 1part binder). **B.t.i. compositions applied as an agglomerated cubetteat ca. 5 lb/acre.

EXAMPLE 4

A controlled delivery system for solvent-base (i.e., acetone)precipitation was developed to agglomerate an aqueous admixturesuspension of a joint-function carrier/coating water soluble polyvinylalcohol film (MonoSol® 8000 series) and B.t.i. (Acrobe® Biolarvicide).The procedure utilized a series of acetone washes to rapidly congeal theaqueous homogeneous mixture of polyvinyl alcohol film and B.t.i. into aunified mass by removing the water entrapped within the solid. Polyvinylalcohol films (specific gravity greater than one) are soluble in waterand insoluble in acetone while B.t.i. is suspendible in water butinsoluble in acetone or water.

Compositions were prepared utilizing the following protocol: 12 gpolyvinyl alcohol film (MonoSol® 8000 series) was dissolved in 46.8 gdistilled water in a plastic beaker. 1.2 g Acrobe® Biolarvicide wasmixed with the water-base joint-function carrier/coating with a GE® 420Ahand mixer for ca. 2 minutes. The formulation was poured into 2 ounceglass medicine bottles and vigorously hand shaken for ca. 1 minute. 7 to10 g polyvinyl alcohol film/B.t.i/water formulation was added to aplastic centrifuge tube (ca. 60 ml capacity) containing ca. 35-40 gacetone. The centrifuge tube was capped and vigorously hand shaken tosolidify the polyvinyl alcohol film and B.t.i. into a unified masswithin the aqueous-acetone medium. The solid mass was removed and placedinto 50 ml glass beakers containing ca. 40 g acetone for a series offive one minute washes to remove entrapped water from within the solidmatrix. The solid mass was removed from the acetone and thoroughlyair-dried in a low humidity room (ca. 27-38% RH) for ca. 72 hr. Thesolid compositions were stored in Zip-lock™ bags until bioassay. Theremaining stock formulation of water, polyvinyl alcohol film, and B.t.i.was stored in a refrigerator (ca. 40° F.) for future use.

A series of short-term bioassays were conducted against larvae ofAnopheles, Aedes, and Culex species in fresh and brackish water with2×2×2 mm cubettes that were sectioned from each agglomerated mass ofpolyvinyl alcohol film and B.t.i. (Table 6). An application rate of onecubette (ca. 0.01 g) per bioassay test chamber (i.e., ® gal plasticbeaker) was extrapolated to be ca. 5 lb/surface acre of water (3replications/test). Results indicated that 100% control of surface orsubsurface feeding larvae could be achieved in fresh or brackish waterwithin 1 to 5 days posttreatment. Based on the specific gravity of thecomponents, cubettes were expected to sink upon introduction to freshand brackish water. However, observations indicated that theagglomerated polyvinyl alcohol film compositions initially floated andbegan to solubilize over a 24 hr period, thereby rapidly releasingsignificant quantities B.t.i. from the surface to subsurface areas whilealso retaining B.t.i. in the polyvinyl alcohol film that had spread overthe surface of the water. It appears that air bubbles entrapped withinthe polyvinyl alcohol film matrix during the vigorous admixing procedurein combination with the suspending agents/ surfactants present in theAcrobe® Biolarvicide formulation were responsible for the initialsurface orientation of the cubettes, and the film-forming properties ofthe water soluble cubettes. The data on the rates of mortality ofsurface (i.e., Anopheles spp.) and subsurface (i.e., Aedes and Culexspp.) feeding larvae support the aforementioned observations concerningfilm-forming solubilization of cubettes and release of B.t.i in theexperimental aquatic habitats.

TABLE 6 (Example 4). Coating-Regulated Delivery of Acrobe ® Biolarvicidefrom an Agglomerated Joint-Function Composition* % Control of Larvae atIndicated Post- Mosquito Larval Water treatment Time Period (Days)**Species Instar Quality 1 2 3 4 5 Surface Feeders (Anopheles spp.) An.albimanus 2nd Fresh 70.0 76.7 100.0 — — An. albimanus 2nd Brackish 46.750.0 100.0 — — An. albimanus 3rd Fresh 40.0 46.7 90.0 100.0 — An.albimanus 3rd Brackish 43.3 46.7 100.0 — — An. quadrimaculatus 2nd Fresh93.3 93.3 100.0 — — An. quadrimaculatus 3rd Fresh 30.0 30.0 66.7 90.0100.0 Subsuface Feeders (Aedes and Culex spp.) Ae. taeniorhynchus 2ndBrackish 100.0 — — — — Ae. taeniorhynchus 3rd Brackish 100.0 — — — — Cx.quinquefasciatus 2nd Fresh 100.0 — — — — Cx. quinquefasciatus 3rd Fresh100.0 — — — — *9% Acrobe ® Biolarvicide (w/w) in each controlled releaseB.t.i. composition. Compositions contained a water and solvent-freejoint-function carrier/coating polyvinyl alcohol fllm (91%) andbioactive agent 9%. **B.t.i. compositions applied as agglomeratedcubettes at ca. 5.0 lb/acre.

EXAMPLE 5

A series of short-term controlled release bioassays were also conductedagainst larvae of Anopheles, Aedes, and Culex species in fresh andbrackish water to determine the mosquito-controlling efficacy ofpowdered compositions comprising admixtures of B.t.i. (Vectobac® TP),the insect growth regulator methoprene (Dianex®EC), a joint-actionformulation of Dianex®EC and .B.t.i. (Acrobe®TP) or an organophosphate(Abate®4-E) and a cetyl alcohol coating and hydrophobic silica(Sipernat® D17) carrier. Abate® 4-E was also admixed with a watersoluble polyvinyl alcohol film (MonoSol® 8000 series) joint-functioncarrier/coating to form a solid agglomerated composition that wassectioned into cubettes (ca. 3.5×3.5×4.5 mm). Admixing procedures forformulating these powdered or agglomerated controlled deliverycompositions are presented in Table 7.

Results of bioassays with the powdered and cubette compositionsindicated that controlled delivery of formulations of an organophosphate(specific gravity greater than one), insect growth regular (specificgravity less than one) and a bacteria (specific gravity greater thanone)/insect growth regulator (specific gravity less than one) from ahydrophobic silica or joint-function polyvinyl alcohol film carrier wasregulated by the physico-chemical characteristics of the cetyl alcoholor polyvinyl alcohol film coatings admixed into the formulation (Table8). The data indicated that the surface-active powdered or agglomerated(cubette) floating compositions were effective in delivering at varyingrates one or more bioactive agents at and/or below the surface of thewater where Anopheles, Aedes, and Culex species could be targeted by thespecific type(s) of bioactive agent(s) released from the carrier intodifferent vertical and horizontal areas of the water column. One hundredpercent control of all immature mosquitoes was observed within 1 to 21days posttreatment when the compositions were applied as a directtreatment or pretreatment in fresh or brackish water at an extrapolatedrate of 2.5 lb/surface acre of water for powdered compositions and 5.0lb/surface acre of water for agglomerated compositions.

TABLE 7 (Example 5). Formulation Components in Powdered and AgglomeratedControlled Delivery Compositions Composition Concentration of CodeAdmixtures in Powdered and Agglomerated Compositions PowderedCompositions* D 0.5 g methoprene (Dianex ® EC) + 10 g cetyl alcohol +89.5 g hydrophobic silica (Sipernat ® D17) E 5 g 0.5 g methoprene(Dianex ® EC) + 10 g cetyl alcohol + 89.5 g hydro-phobic silica(Sipernat ® D17) + 5 g 5 g B.t.i. (Acrobe ® TP) + 10 g cetyl alcohol +85 g hydrophobic silica (Sipernat ® D17) F 5 g B.t.i. (Vectobac ® TP) +10 g cetyl alcohol + 85 g hydrophobic silica (Sipernat ® D17) G 0.5 gtemephos (Abate ® 4-E) + 10 g cetyl alcohol + 89.5 g hydrophobic silica(Sipernat ® D17) Agglomerated Compositions** H 0.3 g temephos (Abate ®4-E) + 12 g polyvinyl alcohol film (MonoSol ® 8000 series) + 47.7 gdistilled water + acetone bath series *Cetyl alcohol (heated to 60° C.)was added to 300 g acetone and mixed for ca. 5 miutes with a GE ® odel420A hand mixer in a ½ gal plastic beaker. B.t.i., methoprene ormethoprene and B.t.i. or temephos was slowly added to the solvent-baseformulations of coating while mixing for an additional 5 minutes.Hydrophobic silica was added to each solvent-base bioactiveagent/coating formulation while mixing was continued for ca. 3 hr todrive off the acetone and assure that # the silica was uniformlyencapsulated with the homogeneous mixture of each bioactive agent andcoating. Two bioactive agents were combined into a single formulation byadmixing each bioactive agent/coating/carrier formulation at a 1:1mixing ratio. Each powdered composition was placed in a low humidityroom (ca. 27-38% RH) for ca. 4 hr to assure volatilization of thesolvent. The dry powdered compositions were stored in zip-lock bags orglass bottles until being utilized in mosquito # bioassays. **Polyvinylalcohol film was dissolved in distilled water in a plastic beaker.Temephos was mixed with the aqueous formulation of joint-functioncoating/carrier with a GE ® Model 420A hand mixer for ca. 2 minutes. Theinsecticide formulation was poured into 2 ounce glass medicine bottlesand vigorous shaken by hand for ca. 1 minute. 7-10 g water-basepolyvinyl alcohol film/temephos formulation was added into a plasticcentrifuge tube (ca. 60 ml capacity) containing ca. # 35-40 g acetone.The centrifuge tube was capped and vigourous hand shaken to solidify thepolyvinyl alcohol film and B.t.i. admixture into a unified mass withinthe aqueous-acetone medium. The solid mass was removed and placed into50 ml glass beakers containing ca. 40 g acetone for a series of five oneminute washes to remove entrapped water from within the solid matrix.The solid mass was removed from the acetone and thoroughly air-dried ina low humidity room (ca. 27-38% RH) for ca. # 72 hr. The solidcompositions were stored in zip-lock bags or glass bottles until beingused for mosquito bioassays. Remaining stock formulation of water,polyvinyl alcohol, and temephos was stored in a refrigerator (ca. 40°F.) for future use.

TABLE 8 (Example 5). Coating-Regulated Delivery of Dianex ® EC, Dianex ®EC/Acrobe ® TP, Vectobac ® TP or Abate ® 4-E from Powdered orAgglomerated Compositions* Mosquito Larval Water No. Days to Achieve100% Control of Species Instar Quality Larvae, Pupae, and/or EmergingAdults Powdered Composition - Dianex ® EC (0.5% AI Formulation) - Code DAn. albimanus 1st Fresh 21** An. albimanus 1st Brackish 20** Ae. aegypti3rd Fresh 16  Ae. taeniorhynchus 3rd Brackish 14  Powdered Composition -Dianex ® EC/Acrobe ® TP (0.5%/5% AI 1:1 Formulation) - Code E Ae.taeniorhynchus 3rd Brackish   Cx. quinquefasciatus 3rd Fresh 18 Powdered Composition - Vectobac ® TP (5% AI Formulation) - Code F Cx.quinquefasciatus 2nd Fresh 10  Powdered Composition - Abate ® 4-E (0.5%AI Formulation) - Code G An. albimanus 1st Fresh 1  An. albimanus 1stFresh 2** An. albimanus 1st Brackish 1  An. albimanus 1st Brackish 2**Ae. taeniorhynchus 3rd Brackish 1  Cx. quinquefasciatus 3rd Fresh 1 Agglomerated Composition - Abate ® 4-E (0.5% AI Aqueous/2.4% AI DryFormulation) - Code H An. albimanus 4th Fresh 1  An. albimanus 4thBrackish 1  An. quadrimaculatus 4th Fresh 1  Ae. taeniorhynchus 3rdBrackish 1  Cx. quinquefasciatus 2nd Fresh 1  *Powdered controlledrelease compositions consisted of a cetyl alcohol coating, bioactiveagent(s), and hydrophobic silica carrier. Agglomerated (cubette)controlled release compositions consisted of a water and solvent-freejoint-function polyvinyl alcohol film coating/carrier (97.6%) andbioactive agent (2.4%). Powdered and agglomerated compositions appliedto the water at rates of 2.5 and 5.0 lb/acre, respectively. **Presoaked(pretreatment) in water for 9 days before transfer to bioassaycontainers.

EXAMPLE 6

A series of long-term controlled release transfer-bioassays wereconducted against multiple broods of larvae of Anopheles, Aedes, andCulex species in fresh or brackish water with a variety of powdered oragglomerated compositions composed of one or more bioactive agentshaving differential degrees of specific gravity greater than or lessthan one, one or more coating shaving specific gravities withdifferential degrees of greater than or less than one as well asdifferential degrees of water solubility or insolubility, and a carrierhaving hydrophobic or hydrophilic characteristics, with or without abinder component. Carrier components consisted of either a hydrophobicsilica (Sipernat® D17) or hydrophilic silica (FK 500 LS or Wesslon™ 50).Bioactive agent utilized in the admixture compositions were B.t.i.(Acrobe® TP), C combination of B.t.i. and methoprene (Dianex® EC) ortemephos (Abate® 4-E). Coatings utilized as bioactive agent release rateand release profile regulators were cetyl alcohol (specific gravil lessthan one/insoluble in water), triethyl citrate (Citroflex® 2; specificgravity greater than one/water soluble), acetyltriethyl citrate(Citroflex® A-2; specific gravity greater than one/water soluble),tributyl citrate (Citroflex® 4; specific gravity greater thanone/insoluble in water), acetyltributyl citrate (Citroflex® A-4;specific gravity greater than one/insoluble in water), acetyltri-n-hexyl citrate (Citroflex® A-6; specific gravity greater thanone/insoluble in water), n-butyltri-n-hexyl citrate (Citroflex B-6;specific gravity less than one/insoluble in water), dicyclohexylphthalate (Morflex® 150; specific gravity greater than one/insoluble inwater), butyl phthalyl butyl glycolate (Morflex®190; specific gravitygreater than one/insoluble in water), and tri-hexyl trimellitate(Morflex® 560; specific gravity greater than one/insoluble in water).Binders admixed with selected formulations to assist in agglomeratingthe fine components into larger units (e.g., briquets) were either asulfonated polystyrene polymer (Versa® TL-502), a sulfonated vinyliccopolymer (Narlex® D-82) or a water soluble starch. Components utilizedin the admixing procedures to formulate the controlled releasecompositions are presented in Table 9.

Results of a series of long-term transfer bioassays in fresh andbrackish water against several broods of larvae of Anopheles, Aedes, andCulex species with a variety of powdered and agglomerated (i.e.,cubette) compositions of B.t.i. (Acrobe® TP) or methoprene (Dianex® EC)and B.t.i. have indicated that these controlled release compositions canbe effective in slowly distributing lethal concentrations of a bacteriaand/or insect growth regulator for a prolonged period to surface and/orsubsurface areas of a water column that were readily accessible t thefeeding and/or orientation of various species of larvae (Table 10). Thedata indicated that the direction(s), duration, and rate(s) ofcontrolled release of the bioactive agent(s) in an aquatic habitat werefunctions of the surface or subsurface orientation of the carrier(s),and the type and concentration of coating(s) and bioactive agent(s)utilized in the powdered or agglomerated compositions. The resultsindicated that 100% control of multiple broods of larvae of Anopheles,Aedes or Culex species could be obtained in fresh or brackish water forat least 3-8 weeks when powdered or agglomerated compositions wereapplied to the water at rates of ca. 2.5 and 5.0 lb/acre, respectively.Powdered and agglomerated compositions were still producing 100% controlof larval populations when tests were terminated.

Similar results were obtained against larvae of Aedes, Anopheles andCulex when corn cob granules and BIODAC® granules were used as carriersfor the coating-regulated controlled delivery. bioactive agentcompositions.

TABLE 9 (Example 6). Formulation Components in Powdered and AgglomeratedControlled Delivery Compositions Concentration of Admixtures in Powderedand Agglomerated Composition Code/No. Compositions PowderedCompositions* J (Example 1) 5 g 5 g B.t.i. (Acrobe ® TP) + 10 g cetylalcohol + 85 g hydrophobic silica (Sipernat ® D17) + 5 g 5 g B.t.i.(Acrobe ® TP) + 5 g triethyl citrate (Citroflex ® 2) + 90 g hydrophobicsilica (Sipernat ® D17) 2 (Example 2) 5 g B.t.i. (Acrobe ® TP) + 10 gcetyl alcohol + 85 g hydro- philic silica (FK 500 LS) K 5 g B.t.i.(Acrobe ® TP) + 5 g triethyl citrate (Citroflex ® 2) + 90 g hydrophilicsilica (Wesslon ™ 50) L 5 g B.t.i. (Acrobe ® TP) + 5 g acetyltriethylcitrate (Citroflex ® A-2) + 90 g hydrophilic silica (Wesslon ™ 50) M 5 gB.t.i. (Acrobe ® TP) + 5 g tributyl citrate (Citroflex ® 4) + 90 ghydrophilic silica (Wesslon ™ 50) N 5 g B.t.i. (Acrobe ® TP) + 5 gtriethyl citrate (Citroflex ® 2) + 90 g hydrophobic silica (Sipernat ®D17) O 5 g B.t.i. (Acrobe ® TP) + 5 g acetytriethyl citrate (Citroflex ®A-2) + 90 g hydrophobic silica (Sipernat ® D17) P 5 g B.t.i. (Acrobe ®TP) + 5 g tributyl citrate (Citroflex ® 4) + 90 g hydrophobic silica(Sipernat ® D17) Q 5 g B.t.i. (Acrobe ® TP) + 5 g acetyltributyl citrate(Citroflex ® A-4) + 90 g hydrophobic silica (Sipernat ® D17) R 5 gB.t.i. (Acrobe ® TP) + 5 g acetyltri-n-hexyl citrate (Citroflex ® A-6) +90 g hydrophobic silica (Sipernat ® D17) S 5 g B.t.i. (Acrobe ® TP) + 5g n-butyltri-n-hexyl citrate (Citroflex ® B-6) + 90 g hydrophobic silica(Sipernat ® D17) T 5 g B.t.i. (Acrobe ® TP) + 2.5 g triethyl citrate(Citroflex ® 2) + 2.5 g tributyl citrate (Citroflex ® 4) + 90 ghydrophobic silica (Sipernat ® D17) U 5 g B.t.i. (Acrobe ® TP) + 5 gdicyclohexyl phthalate (Morflex ® 150) + 90 g hydrophobic silica(Sipernat ® D17) V 5 g B.t.i. (Acrobe ® TP) + 5 g butyl phthalyl butylglycolate (Morflex ® 190) + 90 g hydrophobic silica (Sipernat ® D17) W 5g B.t.i. (Acrobe ® TP) + 5 g tri-n-hexyl trimellitate (Morflex ® 560) +90 g hydrophobic silica (Sipernat ® D17) E (Example 5) 5 g 5 g B.t.i.(Acrobe ® TP) + 10 g cetyl alcohol + 85 g hydro- phobic silica(Sipernat ® D17) + 5 g 0.5 g methoprene (Dianex ® EC) + 10 g cetylalcohol + 89.5 g hydrophobic silica (Sipernat ® D17) AgglomeratedCompositions** A (Example 3) 5 g 5 g B.t.i. (Acrobe ® TP) + 10 g cetylalcohoi + 85 g hydrophobic silica (Sipernat ® D17) + 5 g sulfonatedpoly- styrene polymer (Versa ® TL-502) B (Example 3) 5 g 5 g B.t.i.(Acrobe ® TP) + 10 g cetyl alcohol + 85 g hydro- phobic silica(Sipernat ® D17) + 5 g sulfonated vinylic copolymer (Narlex ® D-82) C(Example 3) 5 g 5 g B.t.i. (Acrobe ® TP) + 10 g cetyl alcohol + 85 ghydro- phobic silica (Sipernat ® D17) + 5 g soluble starch *Cetylalcohol (heated to 60° C.), triethyl citrate, a combination of triethylcitrate and cetyl alcohol, acetyltriethyl citrate, tributyl citrate,acetyltributyl citrate, acetyltri-n-hexyl citrate, n-butyltri-n-hexylcitrate, dicyclohexyl phthalate, butyl phthalyl butyl glycolate,tri-n-hexyl trimellitate, or a 1:1 combination of triethyl citrate andtributyl citrate was added to 300 g acetone and mixed for ca. 5 minutes(speed #6; wire whip) with a KitchenAid ® KSM 90 hand mixer # in a 4½ qtstainless steel bowl or with a GE ® hand mixer Model 420A. B.t.i. or aB.t.i. and methoprene mixture was slowly added to the solvent-baseformulations of coatings while mixing (stir, speed #6, wire whip) wascontinued for ca. 5 minutes. Hydrophobic or hydrophilic silica was addedto each solvent-base bioactive agent/coating formulation while mixing(stir, speed #6, wire whip, flat beater blade) was continued for ca. 3hr to drive office the acetone and # assure that the silica wasuniformly encapsulated with the homogeneous mixture of each bioactiveagent and coating. Two bioactive agents were combined into a singleformulation by admixing each bioactive agent/coating/carrier formulationat a 1:1 mixing ratio. Each powdered composition was placed in a lowhumidity room (ca. 27-38% RH) for ca. 3 to 4 hr to assure volatilizationof the solvent. The dry powdered compositions were stored in zip-lockbags or glass bottles until being # utilized in mosquito bioassays.**Cetyl alcohol (heated to 60° C.) was added to 300 g acetone and mixedfor ca. 5 minutes with a GE ® Model 420A hand mixer in a ½ gal plasticbeacker. B.t.i. was slowly added into the solvent-base formulation ofcoating while mixing for an additional 5 minutes. Hydrophobic silica wasmixed with the other components while mixing was continued for ca. 3 hrto drive off the acetone and assure a homogeneous dry mixture of allcomponents. The powdered composition was placed # in a low humidity room(ca. 27-38% RH) for ca. 4 hr to assure volatilization of solvent. Aratio of one part of this powdered 3-part bioactiveagent/coating/carrier formulation was mixed with one part binder(sulfonated polystyrene polymer, sulfonated vinylic copolymer or solublestarch) for ca. 5 minutes. The 1:1 composition was then hand compactedinto 25 × 20 × 5 mm vinyl specimen molds (Cryomold ®) and placed in ahigh humidity curing room (ca. 80% RH and # 80° F.) for ca. 96 hr. Moldscontaining each composition were then transferred to a drying room (ca.27-38% RH, 76-79° C.) for an additional 96 hr. The dry solidifiedbriquet compositions in each mold were stored in plastic zip-lock bags.Subsections of each briquet (i.e., ca. 3.5 × 3.5 × 4.5 mm cubettes) wereutilized in the bioassays. One cubette (ca. 0.01 g) was utilized againstmosquito larvae in each bioassay test chamber (3replications/agglomerated # composition).

TABLE 10 (Example 6). Coating-Regulated Controlled Delivery of Acrobe ®TP or Acrobe ® TP/Dianex ® EC from Powdered or AgglomeratedCompositions* No. Days to Achieve 100% Larval Control at Larval Instar/Composition Transfer Period Mosquito Composition Transfer WaterComposition (No. Days Between Transfers) Test Duration Species Period(T)** Quality Code/No. T₀ (T₀-T₁) T₁ (T₁-T₂) T₂ (Days)*** PowderedCompositions - ACROBE ® TP (5% AI Formulation) Ae. aegypti 3rd/T₀, T₁Fresh J 3 (31) 6 — — 40 Ae. taeniorhynchus 3rd/T₀, 1st/T₁ Brackish 2****1 (14) 4 — — 31 Ae. taeniorhynchus 2nd/T₀, T₁ Brackish K***** 7 (15) 9 —— 61 Ae. taeniorhynchus 2nd/T₀, T₁ Brackish L***** 2 (20) 4 — — 56 Ae.taeniorhynchus 2nd/T₀, T₁ Brackish M***** 2 (20) 9 — — 61 An. albimanus2nd/T₀, T₁ Fresh N 3 (17) 5 — — 25 An. albimanus 2nd/T₀, T₁ Fresh O 1(19) 1 — — 21 An. albimanus 2nd/T₀, T₁ Fresh P 1 (19) 4 — — 24 An.albimanus 2nd/T₀, T₁ Fresh Q 1 (19) 2 — — 22 An. albimanus 2nd/T₀, T₁Fresh R 1 (19) 1 — — 21 An. albimanus 2nd/T₀, T₁ Fresh S 2 (18) 1 — — 21An. albimanus 2nd/T₀, T₁ Fresh T 1 (19) 1 — — 21 An. albimanus 2nd/T₀,T₁ Fresh U 1 (19) 1 — — 21 An. albimanus 2nd/T₀, T₁ Fresh V 1 (19) 3 — —23 An. albimanus 2nd/T₀, T₁ Fresh W 1 (19) 1 — — 21 An. albimanus2nd/T₀, T₁ Brackish N 3 (17) 8 — — 28 An. albimanus 2nd/T₀, T₁ BrackishO 1 (19) 10 — — 30 An. albimanus 2nd/T₀, T₁ Brackish P 1 (19) 15 — — 35An. albimanus 2nd/T₀, T₁ Brackish Q 1 (19) 6 — — 26 An. albimanus2nd/T₀, T₁ Brackish R 1 (19) 2 — — 22 An. albimanus 2nd/T₀, T₁ BrackishS 1 (19) 7 — — 27 An. albimanus 2nd/T₀, T₁ Brackish T 1 (19) 1 — — 21An. albimanus 2nd/T₀, T₁ Brackish U 10 (10) 8 — — 28 An. albimanus2nd/T₀, T₁ Brackish V 1 (19) 5 — — 25 An. albimanus 2nd/T₀, T₁ BrackishW 1 (19) 2 — — 22 Powdered Compositions - ACROBE ® TP (5% AIFormulation) Cx. quinquefasciatus 2nd/T₀, T₁ Fresh K 2 (17) 7 (26) 13 65Cx. quinquefasciatus 2nd/T₀, T₁ Fresh L 1 (18) 14 (19) 14 66 Cx.quinquefasciatus 2nd/T₀, T₁ Fresh M 2 (17) 5 (28) 17 69 PowderedCompositions - ACROBE ® TP/DIANEX ® EC (5%/10.5% AI 1:1 Formulation) Ae.taeniorhynchus 3rd/T₁, T₂ Brackish E 4 (17) 13 — — 34 AgglomeratedCompositions - ACROBE ® TP (5% AI Formulation) An. albimanus 2nd/T₀, T₁;1st/T₂ Fresh A 2 (12) 3 (21) 9 47 An. albimanus 2nd/T₀, T₁; 1st/T₂ FreshB 1 (13) 3 (21) 8 46 An. albimanus 2nd/T₀, T₁; 1st/T₂ Fresh C 9 (05) 4(20) 7 45 An. albimanus 2nd/T₀, T₁; 1st/T₂ Brackish A 2 (12) 8 (16) 1 53An. albimanus 2nd/T₀, T₁; 1st/T₂ Brackish B 2 (12) 3 (21) 16 54 An.albimanus 2nd/T₀, T₁; 1st/T₂ Brackish C 7 (07) 1 (23) 18 56 *Powderedand agglomerated controlled release compositions of Acrobe ® TP orAcrobe ® TP/Dianex ® EC applied at rates of ca. 2.5 and 5.0 lb/acre,respectively. **T₀ = Initial composition introduction; T_(1,2) = No.post-introduction composition transfers. ***Compositions remained inwater for test duration as a pretreatment without larvae or duringlarvae challenges in T₀, T₁, and T₂, and between transfer periods T₀—T₂with dead larvae/pupae. Compositions briefly removed with a 100 meshsieve to transfer formulations from T₀, to T₁ and T₁ to T₂ testchambers. Tests terminated even though compositions were still effectivein producing 100% control of immatures. ****Powdered compositionsinitially introduced into water for 12 days without larvae(pretreatment) before being transferred into T₀ test chamber withlarvae. *****Powdered compositions initially introduced into water for30 days without larvae (pretreatment) before being transferred into T₀test chamber with larvae.

EXAMPLE 7

A series of short-term bioassays were conducted in fresh or brackishwater against larvae of Anopheles, Aedes, and/or Culex species withcontrolled release compositions comprising admixtures of the insectgrowth regulator methoprene (Dianex®EC), the bacteria B.t.i. (Acrobe®TP) or an experimental monomolecular surface film (POE(2) IsostearylAlcohol), one or more hydrophobic (FK 500 LS, Sipernat® 22S, Wesslon™)and/or hydrophobic (Sipernat®D17) silica or hydrophobic “pin chips”(SeaSweep®) carriers, and one or more cetyl alcohol (specific gravityless than one, insoluble in water), triethyl citrate (Citroflex®2;specific gravity greater than one, soluble in water), tributyl citrate(Citroflex®4; specific gravity greater than one, insoluble in water),and/or n-butyryl tri-n-hexyl citrate (Citroflex® B-6; specific gravityless than one, insoluble in water) coatings, and/ or one or morejoint-function polyvinyl alcohol films (specific gravity greater thanone, soluble in water) that can act as a coating and carrier. Allcoatings showed differential surface spreading potentials when appliedto the water. Specific formulation components for each of thecompositions utilized in these bioassays are presented.in Table 11.

Results of larval bioassays against single or mixed species populationsindicated that the initial orientation of delivery of an insect growthregulator, bacteria or monomolecular surface film from a controlleddelivery composition was dictated by the surface and/or subsurfacecharacteristics of the bioactive agent/coating-encapsulated carrier(s)in an aquatic habitat (Table 12). Changes over time in the initialorientation or direction and rate of delivery in a water column weredetermined by the specific gravity, solubility, and film-formingcharacteristics of the coating agent(s) and bioactive agent(s)encapsulated on the carrier(s).

The data indicated that 100% larval control of mixed populations ofAnopheles and Culex species occurred in all powdered B.t.i. formulations(2.5 lb/acre application) in 24 hr posttreatment; however, the rates ofcontrol within the 24 hr period were observed to be formulation (i.e.,coating) dependent. Complete control (i.e., 100%) of larvae of Aedeswith two powdered compositions of POE (2) Isostearyl Alcohol (5 lb/acreapplication) was observed in 11 and 13 days posttreatment while 100%control of larvae of Culex mosquitoes exposed to two “pin chip”compositions of methoprene (2.5 lb/acre application) was observed in 28and 30 days posttreatment. Mixed populations of Anopheles larvae werekilled in both water qualities within 24 hr posttreatment with allpolyvinyl alcohol film compositions. These agglomerated admixtureformulations (i.e., cubettes) initially floated and differentiallysolubilized within 24 hr. It appears that air entrapped within thepolyvinyl alcohol matrices caused the formulations to float. Cubetteagglomeration and hardness were affected by the type of solvent utilizedin the fabrication process. Polyvinyl alcohol film(s) and B.t.i.compositions (Codes 12, 13, 14) were secondarily admixed with 0.15-0.5 gsoluble starch, Carboset®514H, Carbopol® ETD 2001, Narlex®D-82,Versa®TL-502, Citroflex® A-2, Morflex® 150, FK 500 LS, Sipernat®D17,ethoxylated alcohols, and/or salts (e.g., NaCl Instant Ocean®).Additions of one or more binder, coating agents, carriers, and/oradditional ingredients to the formulations indicated in Codes 12, 13, 14were observed to significantly affect component dissociation from thecubettes as well as the surface/subsurface orientation of the cubettes/cubette components in the water column. The type of salt(s)utilized in the aqueous formulation and the type of solvent(s) utilizedin the aqueous agglomeration and drying protocols were observed to havea significant affect on the agglomeration performance and rigidity ofthe matrices containing the additional admixture ingredients.

TABLE 11 (Example 7). Formulation Components in Powdered, Chipped orAgglomerated Controlled Delivery Compositions Composition Concentrationof No. Admixtures in Powdered and Chipped Compositions PowderedCompositions*  5 10 g B.t.i. (Acrobe ® TP) + 20 g cetyl alcohol + 85 ghydrophobic silica (Sipernat ® D17) + 85 g hydrophilic silica (Wesslon ™)  6 10 g B.t.i. (Acrobe ® TP) + 10 g cetyl alcohol + 10 triethylcitrate (Citroflex ® 2) + 85 g hydrophobic silica (Sipernat ® D17) and85 g hydrophilic silica (Wesslon ™ )  7 10 g B.t.i. (Acrobe ® TP) + 10 gcetyl alcohol + 10 g n-butyrltri-n-hexyl citrate (Citroflex ® B-6) + 85g hydrophobic silica (Sipernat ® D17) + 85 g hydrophilic silica(Wesslon ™ )  8 24.75 g Monomolecular Surface Film (POE(2) IsostearylAlcohol) + 0.25 g triethyl citrate (Citroflex ® 2) + 75 g hydrophilicsilica (Sipernat ® 22S)  9 24.75 g Monomolecular Surface Film (POE(2)Isostearyl Alcohol) + 0.25 g tributyl citrate (Citroflex ® 4) + 75 ghydrophilic silica (Sipernat ® 22S) Chipped Compositions** 10 5 gmethoprene (Dianex ® EC) + 5 g triethyl citrate (Citroflex ® 2) + 90 g“pin chips” (SeaSweep ® ) 11 5 g methoprene (Dianex ® EC) + 5 gn-butyrltri-n-hexyl citrate (Citroflex ® B-6) + 90 g “pin chips”(Seasweep ® ) Agglomerated Compositions*** 12 3 g B.t.i. (Acrobe ®Biolarvicide) + 12 g polyvinyl alcohol film (MonoSol ® 8000 series) + 45g distilled water + acetone, methyl ethyl ketone or 2-propanol bathseries 13 3 g B.t.i. (Acrobe ® Biolarvicide) + 12 g polyvinyl alcoholfilm (MonoSol ® 7000 series) + 45 g distilled water + acetone, methylethyl ketone or 2-propanol bath series 14 3 g B.t.i. (Acrobe ®Biolarvicide) + 6 g polyvinyl alcohol film (MonoSol ® 8000 series) + 6 gpolyvinyl alcohol film (MonoSol ® 7000 series) + 45 g distilled water --acetone, methyl ethyl ketone or 2-propanol bath series *Cetyl alcohol(heated to 60° C.), triethyl citrate, tributyl citrate, and/orn-butyrltri-n-hexyl citrate was added to 600 g acetone and mixed for ca.5 minutes (speed #6, wire whip) with a KitchenAid ® KSM 90 hand mixer ina 4½ qt stainless steel bowl. B.t.i. or the experimental monomolecularsurface film was slowly added to the solvent-base formulations ofcoatings while mixing (stir, speed #6, wire whip) was continued for ca.5 minutes. Hydrophobic and/or # hydrophilic silica was added to eachsolvent-base bioactive agent/coating formulation while mixing (stir,speed #6, wire whip, flat beater blade) was continued for ca. 3 hr todrive off the acetone and as sure that each silica was uniformlyencapsulated with the homogeneous mixture of each bioactive agent andcoating(s). Each powdered composition was placed in a low humidity room(ca. 27-38% RH) for ca. 3 to 4 hr to assure volatilization of thesolvent. The dry powdered compositions # were stored in zip-lock bags orglass bottles until being utilized in mosquito bioassays. **Triethylcitrate or n-butyrltri-n-hexyl citrate and methoprene were added to 300g acetone in 1000 ml Nalgene bottles and placed on a paint shaker(Miller Strokemaster ™ ) for ca. 1 hr to assure that the insect growthregulator formulation was well mixed “Pin chips” (ca. 2 × 8 mm) wereadded to the bottles containing the acetone/methoprene/citrateformulations and hand shaken for ca. 10-30 seconds to assure that the“pin chips” were saturated with the # formulations. “Pin chips”continued to soak in the formulations for ca. 18 hr before being removedon sieves and placed in a drying room (ca. 27-38% RH) for ca. 24 hr toassure volatilization of the acetone. The dry “pin chip” formulationswere placed into zip-lock bags until being used for mosquito bioassays.***One or more polyvinyl alcohol films were dissolved in distilled waterin a plastic beaker. B.t.i. was mixed with the aqueous formulation ofjoint-function coating/carrier with a KitchenAid ® KSM 90 hand mixer forca. 1 to 2 minutes. The insecticide formulations were poured into 2ounce glass medicine bottles and vigorously shaken by hand for ca. 1minute. 7-10 g water-base polyvinyl alcohol films/B.t.i. formulationswere added to plastic centrifuge tubes (ca. 60 ml # capacity) containingca. 35-40 g acetone, methyl ethyl ketone or 2 propanol. The centrifugetube was capped and vigorously hand shaken to solidify to polyvinylalcohol film(s) and B.t.i. admixtures into a unified mass within theaqueous-acetone, aqueous-methyl ethyl ketone or aqueous-2-propanolmedium. The solid mass from each tube was removed and placed into 50 mlglass beakers containing ca. 40 g acetone, methyl ethyl ketone or2-propanol for a series of five one minute washes to # remove entrappedwater from the solid matrix. The solid mass was removed from eachacetone, methyl ethyl ketone or 2-propanol bath and thoroughly air-driedin a low humidity room (ca. 27-38% RH) for ca. 72 hr. The solidcompositions were stored in zip-lock bags or glass bottles until beingused for mosquito bioassays. Remaining stock formulations of water,polyvinyl alcohol film(s), and B.t.i. were stored in a refrigerator (ca.40° F.) for future use.

TABLE 12 (Example 7). Coating-Regulated Delivery of Acrobe ® TP,Dianex ® EC or POE(2) Isostearyl Alcohol from Powdered, Chipped orAgglomerated Compositions Mosquito Larval Water Composition No. Days toAchieve 100% Control of Species Instar Quality No. Larvae, Pupae and/orEmerging Adults Powdered Composition - Acrobe ® TP (5% AI Formulation)*An. albimanus/ 2nd/ Fresh 5 1 Cx. quinquefasciatus 2nd An. albimanus/2nd/ Fresh 6 1 Cx. quinquefasciatus 2nd An. albimanus/ 2nd/ Fresh 7 1Cx. quinquefasciatus 2nd An. albimanus/ 2nd/ Brackish 5 1 Cx.quinquefasciatus 2nd An. albimanus/ 2nd/ Brackish 6 1 Cx.quinquefasciatus 2nd An. albimanus/ 2nd/ Brackish 7 1 Cx.quinquefasciatus 2nd Powdered Compositions - POE(2) Isostearyl Alcohol(25% AI Formulation)** Ae. taeniorhynchus 3rd Brackish 8 11 Ae.taeniorhynchus 3rd Brackish 9 13 Chipped Compositions - Dianex ® EC (5%AI Formulation)*** Cx. quinquefasciatus 2nd Fresh 10 26 Cx.quinquefasciatus 2nd Fresh 11 23 Agglomerated Compositions - Acrobe ® TP(20% AI Formulation)**** An. albimanus 2nd Fresh 12 1 An. albimanus 2ndFresh 13 1 An. albimanus 2nd Fresh 14 1 An. albimanus 2nd Brackish 12 1An. albimanus 2nd Brackish 13 1 An. albimanus 2nd Brackish 14 1*Powdered controlled delivery compositions of B.t.i., one or more cetylalcohol and/or citrate coatings, and one or more hydrophobic and/orhydrophilic silica carriers were applied at a rate of ca. 2.5 lb/acre(i.e., 0.005 g/bioassay test chamber). **Powdered controlled deliverycompositions of a monomolecular surface film, a citrate coating, and ahydrophilic silica carrier were applied at a rate of ca. 5 lb/acre(i.e., 0.01 g/bioassay test chamber). ***Chipped controlled deliverycompositions of methoprene, a citrate coating, and a hydrophobic “pinchip” carrier were applied at a rate of ca. 2.5 lb/acre (i.e., 5 “pinchips”; 0.005 g/bioassay test chamber). ****Agglomerated controlleddelivery compositions (i.e., cubettes) of B.t.i. (20%) and a water andsolvent-free joint-function polyvinyl alcohol film coating/carrier (80%)were applied at a rate of ca. 5 lb/acre (i.e., one, 0.01 gcubette/bioassay test chamber). Aqueous insecticide formulationsfabricated into solid mass by a series of solvent precipitation andevaporation procedures.

EXAMPLE 8

In another evaluation, 0.01, 0.05, and 0.1 g Pemulen® TR-1 or Pemulen®TR-2 acrylic copolymer suspending agents were added to 47.5 g distilledwater in 50 ml glass medicine bottles and vigorously shaken by hand forca. 2-3 minutes to form a homogeneous mixture. 2.5 g of the powderedcontrolled release compositions of B.t.i. (Acrobe® TP), one or morehydrophobic and/or hydrophilic silica carriers and one or moreCitroflex®, Morflex® and/or cetyl alcohol coatings (Examples 1-7) wereadded to each of the aqueous acrylic copolymer formulations and placedon a mechanical shaker and vigorously mixed for ca. 5 minutes to assurethat the silica-base compositions were uniformly suspended throughoutthe water column. Results of the suspendability tests indicated thatthese powdered compositions could be readily dispensed in water withconventional spray equipment. Suspension of compositions in petroleum ornonpetroleum oils for spray application is also proposed.

EXAMPLE 9

In another test, an aqueous formulation of the aquatic herbicideAquathol®K (dipotassium salt of endothall) was admixed with ajoint-function (carrier/coating) polyvinyl alcohol film (MonoSol® 8000series, M-7030, M-8533 or M-8030) and agglomerated into a solidifiedcontrolled delivery mass in a series of solvent precipitation andevaporation procedures. The admixing protocol utilized was similar toprocedures described in Examples 4, 5, and 7. As indicated in theearlier examples, polyvinyl alcohol film (specific gravity greater thanone) is soluble in water (temperature dependent) but insoluble in mostorganic and inorganic solvents, hydrocarbons or oils. These propertiesare also similar for polyethylene oxide and hydroxypropyl methylcellulose water-soluble films. MonoSol® 8000 series was obtained fromthe manufacturer as solid sheets/pouches and dissolved in water (20%polyvinyl alcohol film) while MonoSol® M-7030, M-8533 and M-8030 wereobtained as water-base solutions (16.1-16.4% polyvinyl alcohol film).

The following formulations were utilized in fabricating thejoint-function polyvinyl alcohol compositions of Aquathol®K: CompositionAK1—4 g dipotassium salt of endothall (Aquathol®K)+12.5 g polyvinylalcohol film (MonoSol® 8000 series)+46 g distilled water+acetone bathseries; Composition AK2—2.0 g dipotassium salt of endothall(Aquathol®K)+7.4 g polyvinyl alcohol film (MonoSol® M-7030)+40.6 gdistilled water+acetone bath series; Composition AK3—2 g dipotassiumsalt of endothall (Aquathol®K)+7.3 g polyvinyl alcohol film (MonoSolo®M-8533) +40.7 distilled water +acetone bath series; and CompositionAK4—2 g dipotassium salt of endothall (Aquathol®K)+7.3 g polyvinylalcohol film (MonoSol® M-8030) +40.7 g distilled water+acetone bathseries.

The dried agglomerated briquet compositions of AK1, AK2, AK3, and AK4consisted of 24.4, 21.5, 21.7, and 21.8% (w/w) dipotassium salt ofendothall, respectively. Commercial Aquathol®K granules contain only10.1% dipotassium salt of endothall.

Results of the admixing procedures indicated that high levels ofAquathol®K can be agglomerated into solid polyvinyl alcohol-basecompositions for fast-release application into an aquatic habitat forcontrol of nuisance vegetation. All compositions solubilized in freshwater within 2 hr of introduction and showed differential degrees offloating or sinking depending on the type and/or concentration ofpolyvinyl alcohol utilized in the formulation.

Loading levels were significantly higher than the standard commerciallyavailable granular Aquathol®K product (i.e., 10.1% dipotassium salt ofendoth all), and therefore, a lesser amount (on a weight basis) per acreof MonoSol®/Aquathol®K would be required to treat an acre of aquaticweeds when compared to the amount or weight of conventional Aquathol®Kgranular product needed per acre to be equivalent to the concentrationof dipotassium salt of endothall in the composition. The resultsindicated that significantly higher loading levels can be obtained withthe polyvinyl alcohol-base protocol. Addition of one or more coatings,surfactants, binders, and the like is expected to change the controlledrelease profiles of the compositions. Any herbicide can be fabricatedinto a solid controlled delivery composition utilizing thejoint-function polyvinyl alcohol-base admixing protocol.

EXAMPLE 10

In this example, aqueous formulations of the insect growth regulatorpyriproxyfen (Nylar® 10% EC) was admixed with a gum/molasses-base baitand a joint-function (carrier/coating) polyvinyl alcohol film (MonoSol®8000 series) and agglomerated into three types of unified solid masses(i.e., sheets, coatings, and extrusions). The admixing and fabricationprocedures are described in Table 13. In this example, the agglomeratedjoint-function controlled delivery compositions of matter are utilizedto illustrate the present invention, and were designed to target (i.e.,control) a terrestrial pest. Nymphs (7-10 mm) of the German cockroachBlattella germanica (Navy 3 strain) were used as models to demonstratethe efficacy of the agglomerated controlled delivery insecticide-baitcompositions in a terrestrial environment.

A series of long-term transfer bioassays (Table 14) were conducted ingrey polyethylene trays (ca. 51×31×15 cm; Consolidated Plastics,Twinsburg, Ohio). An extruded chamber, a section (85 mm diameter) ofpoured sheet, or a coated vial was placed in one corner of a tray. Theextruded chamber or small section of the poured sheets was placed in a35×10 mm plastic petri dish. One 35×10 mm plastic petri dish containingca. 5.0 g rabbit chow was placed in the opposite corner as an alternatefood source. A cotton-plugged glass vial (40 ml) containing water wasplaced in a 100×15 mm square petri dish and positioned in the center ofthe tray. The top edge of each test container was treated with a borderof petroleum jelly and mineral oil mix to prevent escape of thecockroaches. Twenty-five nymphs of the German cockroach were added toeach tray. Tests were replicated three times with each joint-functioncomposition.

The effects of the Nylar® (i.e., twisted wing and dark pigmentationsterility indices) on the cockroaches were recorded at 24 hrposttreatment intervals. Nylar® effected cockroaches were removed ateach observation period. When 100% of the cockroaches showed growthregulator effects, each bait-insecticide chamber, sheet or vial wastransferred to a new test tray containing new cockroach nymphs, water,and rabbit chow. Tests were terminated if control mortality exceeded 10%or if any normal adult cockroaches were observed after being exposed tothe Nylar/bait/polyvinyl alcohol controlled delivery compositions asnymphs. Tests were conducted in a room maintained at ca. 27° C. and61-80% RH.

It should be noted that similar joint-function controlled deliverycompositions of 0.5% Dursban® 4-E, gum-molasses-bait and polyvinylalcohol showed comparable efficacy against adult (12-14 mm) Germancockroaches. These bait-insecticide compositions are also expected to beeffective against certain species of ants that are attracted to baits.

It is apparent from these terrestrial tests as well as tests performedin an aquatic environment that a variety of single and joint-actioncoating-regulated controlled delivery composition and devices of thepresent invention can be effective in releasing a variety of bioactiveagents (e.g., pesticides) in both aquatic and terrestrial environmentsfor prolonged periods.

TABLE 13 (Example 10). Formulation Components in Agglomerated Joint-Function Controlled Delivery Compositions Composition Concentration ofAdmixtures in Code Agglomerated Joint-Function Compositions ExtrudedChamber Compositions* E1 2.0 g pyripoxyfen (Nylar ® 10% EC) + 39.6 gpolyvinyl alcohol film (MonoSol ® 8000 series) + 0.2 g gum/molasses-base bait + 158.2 distilled water. Poured Sheet Compositions**S1 2.0 g pyripoxyfen (Nylar ® 10% EC) + 39.6 g polyvinyl alcohol film(MonoSol ® 8000 series) + 0.2 g gum/ molasses-base bait + 158.2 gdistilled water. Coated Vial Compositions*** V1 2.0 g pyripoxyfen(Nylar ® 10% EC) + 39.6 polyvinyl alcohol film (MonoSol ® 8000 series) +0.2 g gum/ molasses-base bait + 158.2 distilled water. *Polyvinylalcohol film (2 mil) was dissolved in distilled water in a plasticbeaker. Pyriproxyfen the bait composition were mixed with the aqueousformulation of joint-function coating/carrier in a ½ gal. plastic beakerby hand-stirring with a spatula for ca. 15 min or by mixing theformulation with a KitchenAid ® KSM 90 in a stainless steel bowl for ca.2-5 min (speed #6; wire whip). A series of ca. 9.0 g aliquots of thehomogeneously mixed aqueous insecticide-bait # formulation was pouredinto plastic Peel-A-Way ® tissue embedding molds (2 × 2 × 2 cm). Moldswere placed in a curing/drying room maintained at ca. 25-26° C. and27-38% RH for ca. 10 days to allow slow drying and adhesion of thesemiviscous insecticide-bait to the walls of the embedding molds tocause self-extrusion of the insecticide-bait formulation to form an opencentral pocket or hollow core in each mold. The resultant self-extruded,joint-function # insecticide-bait chambers were ca. the same size andshape as the molds from which they were removed. Each insecticide-baitchamber was open at one end, and was ca. 2 mm in thickness at the bottomand ca. 0.5 mm on each side of the hollow central core. The dryself-extruded insecticide-bait chamber compositions were stored inzip-lock bags until being used in cockroach bioassays. **Polyvinylalcohol film (2 mil) was dissolved in distilled water in a plasticbeaker. Pyriproxyfen and the bait composition were mixed with theaqueous formulation of joint-function coating-carrier in a ½ gal plasticbeaker by hand-stirring with a spatula for ca. 15 min or by mixing theformulation with a KitchenAid ® 90 KSM mixer in a stainless steel bowlfor 2-5 min (speed #6; wire whip). A thin film of the aqueousjoint-function insecticide-bait # composition was poured over the bottomof several Pyrex ® 3 quart pans (33 × 23 × 5 cm). The glass pans wereplaced in a curing/drying room maintained at ca. 25-26° C. and 27-38% RHfor ca. 48 hr. The dry transparent polyvinyl alcohol/bait/Nylar ® 10% ECfilms (ca. 0.1 mm in thickness) were peeled off the bottom of the glasspans in a continuous sheet, placed on aluminum foil, and stored inzip-lock bags until being used in cockroach bioassays. ***Polyvinylalcohol film (2 mil) was dissolved in distilled water in a plasticbeaker. Pyriproxyfen and the bait composition were mixed with theaqueous formulation of joint-function coating-carrier in a ½ gal.plastic beaker by hand-stirring with a spatula for ca. 15 min or bymixing the formulation with a KitchenAid ® KSM 90 mixer in a stainlesssteel bowl for 2-5 min (speed #6; wire whip). A thin film of thesemiviscous insecticide-bait joint-action formulation was # deposited onthe walls of a series of 2 dram screw cap vials (DSA2-10458;Owens-Illinois Glass Co., Toledo, Ohio), by filling each vial to the topwith the homogeneous formulation, and then rapidly pouring theformulation back out. The vials were inverted over a screen tray andallowed to drain the excess formulation for ca. 2 hr. The open vialswere placed in a curing/drying room maintained at ca. 25-26° and 27-38%RH for ca. 24 hr. Vials coated with the dry polyvinyl alcohol/ #bait/Nylar ® 10% EC film were capped and stored in zip-lock bags untilbeing used in cockroach bioassays.

TABLE 14 (Example 10). Coating-Regulated Controlled Delivery of Nylar ®EC from Agglomerated Joint-Function Compositions Nymph Size (mm)/Composition Transfer No. Days to Achieve 100% Nymphal Test DurationGrowth Regulator Effects at Composition Cockroach Period (T)*Composition Transfer Period (No. Days Between Transfers) Species(Days)** Code T₀ (T₀→T₁) T₁ Duration Extruded Chamber Compositions -NYLAR ® 10% EC (0.5% AI Formulation)*** Blatella germanica 7-10/T₀, T₁E1 39 2 50 91 Poured Sheet Composition - NYLAR ® 10% EC (0.5% AIFormulation)**** Blatella germanica 7-10/T₀, T₁ S1 34 2 48 84 CoatedVial Compositions - NYLAR ® 10% EC (0.5% AI Formulation)***** Blatellagermanica 7-10/T₀, T₁ V1 35 2 60 96 *T₀ = Initial CompositionIntroduction; T₁ = No. post-introduction transfers. **Compositionsremained in test chambers until all replicates showed Nylar ® -inducedgrowth regulator effects (i.e., twisted wing/dark pigment abnormalities)in all cockroach nymphs. Compositions were allowed to remain in testchambers for an additional 2-day period (T₀→T₁) before being transferredto a new test chamber containing new nymphs and food. All tests wereterminated at indicated time period even though all joint-functioncompositions were still # effective in producing 100% growth regulatoreffect (= 100% control) in cockroach nymphs. ***Average extruded chambercomposition weight = ca. 1.48 g./chamber. ****Average poured sheetcomposition weight = ca. 0.28 g/sheet. *****Average coating weight incoated vial compositions = ca. .06 g/vial.

EXAMPLE 11

Biodegradable 12/20 mesh cellulose complex granules (Biodac®) and 10/14mesh corn cob granules were selected as matrices for use in thecontrolled delivery system in this study. These carriers are widely usedin agrochemical operations for delivery of a variety of aquatic andterrestrial pesticides.

A series of nontoxic and biodegradable or erodible coating complexesconsisting of a blend of two coatings were formulated with one of thegranular carriers and a Bacillus thuringiensis var. israelensis (BTI)formulation labeled Vetobac® Technical Powder (5000 ITU/mg) or Bactimos®Primary Powder (7000 ITU/mg), or a methoprene formulation labeledDianex® Emulsifiable Concentrate (32.8% S-methoprene). The compositionswere formulated for prolonged subsurface delivery to target Aedestaeniorhynchus larvae in 10%, 50% or 100% artificial sea water (InstantOcean®) or Culex quinquefasciatus in well water purified by reverseosmosis filtration (RO). The preflood or pretreatment potential of thegranules was also evaluated.

A series of stress test granule-transfer bioassays was designed tosimulate pretreatment of flooded semipermanent brackish water habitatsthat initially have no larval breeding and direct treatment of multiplebroods of mosquito larvae in permanent fresh water or semipermanentbrackish/salt water habitats that periodically flood and dry. Bioassayprotocol consisted of challenging the Aedes or Culex species with thegranules composed of Biodac® or corn cobs, a coating complex, and a BTIor methoprene formulation for ca. 90-100 days (Table 15).

TABLE 15⁽¹⁾ Type I = 92.3% Biodac ® + 3.8% Coating Complex A/B + 3.9%Vectobac ® TP Type II = 97.6% Biodac ® + 1.2% Coating Complex C/E + 1.2%Dianex ® EC Type III = 90.4% corn cob + 4.8% Coating Complex A/D + 4.8%Vectobac ® TP Type IV = 90.4% corn cob + 4.8% Coating Complex A/B + 4.8%Bactimos ® PP ⁽¹⁾A/B 1:1 wt. basis formulated as follows: 5 wt % activeagent 5 wt. % coating 90 wt. % carrier Ratio of components in finalproduct reported in Table 15 A = Triethyl citrate B =n-Butyryltri-n-hexyl citrate C = Cetyl alcohol D = Tri-n-butyl citrate E= Dicyclohexyl phthalate

Bioassays were conducted in ½ gal plastic cups containing 1000 ml of RO,10%, 50%, or 100% artificial sea water (Instant Ocean®) and ten 2nd or3rd instar Ae. taeniorhynchus or Cx. quinquefasciatus larvae (i.e., 10larvae=1 brood). Application rates of 4 corn cob-base or 6 Biodac basegranules/cup were equivalent to ca. 5 lbs/acre. Tests were replicated 3times.

Percent mortality was recorded at 24 hr. posttreatment intervals. Thegranules were transferred to new cups containing new larvae at intervalsthat were dependent on the time required to achieve 100% mortality of alarval brood in a particular water quality. The coating complex,bioactive agent, and matrix integrities were stressed throughout agranule-transfer bioassay by an intermittent series of washings,wettings, and drying cycles. A test was terminated before the 90-100 daytest period if a composition did not kill 100% of a larval brood or ifmortality in control cups exceeded 10%. Larvae were fed ground rabbitchow throughout a test series. Tests were conducted in a room maintainedat ca. 27° C.

Results and Discussion

Results of granule-transfer bioassays against Ae. taeniorhynchus (A.T.)and Cx. quinquefasciatus (C.Q.) are presented in Table 16. Controlleddelivery of BTI from Type I, III, and IV granular compositons wasobserved to follow first order or square-root-of-time kinetics whilemethoprene release from Type II granular compositions follow “pseudo”zero-order kinetics. Prolonged mosquito control was related to the typeof coating complex utilized in a formulation.

TABLE 16 Efficacy of Granules Against Mosquito Larvae Granule Habitat*No. Breeds Control Type (Pre, Semi, Perm) Species Controlled Duration(Days) I Pre A.T. 6 105 I Semi A.T. 7 98 I Perm C.Q. 7 105 II Pre A.T. 390 II Semi A.T. 4 94 II Perm C.Q. 4 97 III Pre A.T. 6 104 III Semi A.T.6 107 III Perm C.Q. 7 108 IV Pre A.T. 6 109 IV Semi A.T. 7 98 IV PermC.Q. 6 90 *Pre = Pretreated semipermanent habitat (flood/dry cycles - noinitial larvae); Semi = Direct treatment semipermanent habitat(flood/dry cycles - initial larvae); Perm = Permanent water habitat(Flood cycles only - initial larvae).

The foregoing coating components, bioactive agents and carriercomponents can be selected to control or eliminate various terrestrialorganisms, and especially nuisance plant and animal organisms such asweeds, rodents, insects, and mites, including but not limited tocockroaches, ants, fire ants, termites, and other varieties of bitinginsects, disease carrying insects, parasites and pathogens, crop eatinginsects, parasites and pathogens and wood eating insects. The coatingsthat are selected in this regard are the degradable ones, e.g.biodegradable coatings selected from those listed above, and those thatalso will protect the bioactive agent from degradation, especiallyultraviolet light degradation. The coatings are also selected to releasethe bioactive agent over a period of time so as to increase theeffectiveness of the bioactive agent.

The compositions of the invention can also be utilized in the treatmentof parasitic or insect caused diseases in animals, especially the G.I.tract of animals such as ruminants, by selecting those components of thecomposition that are approved for animal use. When properly administeredthey can be employed to provide time release compositions for thetreatment of various diseases and disorders. Non-bioactive compounds orcompositions can be used in lieu of the bioactive agents for thetreatment of certain disorders such as the treatment of hoven inruminants by means of surfactant silicone compounds. Some non-limitingexamples of other compounds that may be used in the treatment of animalsis disclosed by Drummond et al., Control of Arthropod Pests ofLivestock: A Review of Technology, 1988, CRC Press, Inc. which isincorporated herein by reference.

A variety of medicaments or pharmaceuticals can also be incorporatedinto the time release compositions as trans-dermal patches or implantsfor treatments of disorders or diseases in man and animals.

In the course of preparing the various compositions of the invention itwas further discovered that in many instances the materials employed ascoatings, carriers, and binders were interchangeable. Joint-functioncarrier coating materials have been described, but in the broaderaspects of the invention, the coating, carrier, and binder compounds orcompositions are to be categorized primarily by the way they areemployed in the composition i.e. by the way the function because of theinterchangeability of the various compounds and compositions that areusable in this regard.

In a further embodiment, the invention comprises a composition of mattercomprising a controlled delivery system for one or more fragrance,flavorant or food additive which includes at least one fragrance,flavorant, or food additive and a coating component for regulating thecontrolled release rate and release profile of the fragrance, flavorant,or food additive or combination of fragrance, flavorant, or foodadditive especially the 2, 3 or 4 component combinations of each or withone another. Applicant has previously defined release rate and releaseprofile.

This composition of matter in a further embodiment also includes acarrier component which the applicant previously defined herein.Additionally, the applicant employs joint-function carrier/coatingagents as defined herein in the foregoing fragrance composition ofmatter. Especially suitable coating components comprise the highmolecular weight organic plasticizer materials also as definedpreviously herein.

The invention also includes a method of controlling the delivery of afragrance material by employing the aforesaid fragrance composition ofmatter on a carrier or a substrate, such as paper, building materials,or any surface which a user desires to make more attractive by theemission of a pleasant fragrance or undesirable by means of a repellingfragrance.

Fragrance materials are further defined and listed in The FragranceFoundation Reference Guide, 1992/1993, and subsequent editions, allpublished by the Fragrance Foundation, 145 East 32nd Street, New York,N.Y. 10016-6002, listing over 1100 fragrances which applicantincorporates herein by reference.

Repelling fragrances include by way of example mercaptans and 4-6 carbonatom aliphatic organic acids all of which are described in Kirk-Othmer,Encyclopedia of Chemical Technology, 1st, 2nd, 3rd and 4th Editionsincorporated herein by reference. These fragrances find use in keepingpests from certain areas and also in military applications to denyterritory to hostile forces.

Compositions of matter in further embodiments comprise controlleddelivery systems for one or more flavors, food additives or nutrients,as well as other non-pesticidal bioactive agents.

Carrier and coatings for flavorants, and food additives comprise thoselisted herein and their equivalents that have FDA approval. Packagingnon-ingestible carriers in FDA approved porous materials such as teabags, sanitized fabric enclosures and the like allows their use inapplications where delivery of the flavorant or food additive takesplace by fluid (gas or liquid) extraction from the package.

The invention also comprises a method for delivering a flavorant or foodadditive by means of the coating optionally in combination with thecarrier both described herein.

Risch et al. ACS Symposium Series 590, Encapsulation and ControlledRelease of Food Ingredients American Chemical Society 1995 incorporatedherein by reference describes flavorants and food additives.

The principles, preferred embodiments, and modes of operation of thepresent invention have been described in the foregoing specification.The invention which is intended to be protected here, however, is not tobe construed as limited to the particular forms disclosed, since theseare to be regarded as illustrative rather than restrictive. Variationsand changes may be made by those skilled in the art without departingfrom the spirit of the invention.

What is claimed is:
 1. A process for treating a population of one or more. terrestrial organisms comprising delivering to a terrestrial environment, a composition of matter consisting essentially of a controlled delivery system for treating a population of one or more terrestrial organisms which is an admixture of at least one carrier component in an amount from about 50 % to about 99% by weight, said carrier component consisting essentially of silicas, cellulose fibers, metal oxides, clays, infusorial earth, slag, lava, paper, hydrophobic wood pin chips, waste wood, sawdust, vermiculite, cork, corn cobs, bagasse, seeds, seed hulls, carbon materials, starches, modified starches, carrageenan, algin, xanthates, agar, fluorinated polymeric materials, polyolefins or copolymers thereof, plaster, gypsum, cement, concrete, asphalt, fiber glass, glass, metals, metal alloys, fabrics, mineral aggregate, leather, natural fibers, synthetic fibers, liposomes, lipospheres, or food proteins and combinations thereof, said composition optionally containing a joint-function carrier/coating agent which is a polyvinyl alcohol, polyethylene oxide, hydroxypropyl methyl cellulose, cetyl alcohol or stearyl alcohol, or combinations thereof, and from about 0.0001% to about 50% by weight of a bioactive agent for treating a population of one or more terrestrial organisms, where said bioactive agents are insecticides, toxicants, monomolecular surface films, petroleum oils, insect growth regulators, plant growth regulators, animal growth regulators, microbial control agents, medicaments, pathogens, parasites, bactericides, viricides, fungicides, algaecides, herbicides, nematicides, amoebicides, miticides, acaricides, predicides, schistisomicides, molluscicides, larvicides, pupicides, ovicides, adulticides, nymphicides, attractants, repellents, growth stimulants, feeding stimulants, nutrients, hormones, chemosterilants, pheromones, fragrances, flavorants, food additives and combinations thereof and from about 1.0% to about 50% by weight of at least one organic plasticizer coating component wherein said coating component is water soluble or biodegradable or erodible, for regulating the controlled release rate and release profile of said bioactive agent where said plasticizer is an acetate, adipate, azeleate, benzoate, caprylamide, capramide, caprate, citrate, cocoate, fumarate, glutarate, glycolate, heptanoate, isobutyrate, isophthalate, laurate, linoleate, maleate, mellitate, myristate, octanoate, oleate, palmitate, pelargonate, phosphate, phthalate, ricinoleate, sebacate, stearate, succinate, toluate, tallate, decanoate, or epoxidized vegetable oils, a toluamide, or chlorinated paraffins, for regulating the controlled release rate and release profile of said bioactive agent said components being selected so that said complex will remain in an application site for a period of time sufficient to effectively treat a population of one or more terrestrial organisms and wherein said composition is free of superabsorbent polymers.
 2. A process for treating a population of one or more terrestrial organisms, comprising delivering to a terrestrial environment a composition of matter comprising a complex for treating a population of one or more terrestrial organisms, said complex consisting essentially of at least one controlled delivery system, which is an admixture of at least one carrier component in an amount from about 50% to about 99% by weight said carrier component consisting essentially of silicas, cellulose fibers, metal oxides, clays, infusorial earth, slag, lava, paper, hydrophobic wood pin chips, waste wood, sawdust, vermiculite, cork, corn cobs, bagasse, seeds, seed hulls, carbon materials, starches, modified starches, carrageenan, algin, xanthates, agar, fluorinated polymeric materials, polyolefins or copolymers thereof, plaster, gypsum, cement, concrete, asphalt, fiber glass, glass, metals, metal alloys, fabrics, mineral aggregate, leather, natural fibers, synthetic fibers, liposomes, lipospheres, or food proteins and combinations thereof, said composition optionally containing a joint-function carrier/coating agent which is a polyvinyl alcohol, polyethylene oxide, hydroxypropyl methyl cellulose, cetyl alcohol or stearyl alcohol, or combinations thereof, and from about 0.0001% to about 50% by weight of a bioactive agent for treating a population of one or more terrestrial organisms, where said bioactive agents are insecticides, toxicants, monomolecular surface films, petroleum oils, insect growth regulators, plant growth regulators, animal growth regulators, microbial control agents, medicaments, pathogens, parasites, bactericides, viricides, fungicides, algaecides, herbicides, nematicides, amoebicides, miticides, acaricides, predicides, schistisomicides, molluscicides, larvicides, pupicides, ovicides, adulticides, nymphicides, attractants, repellents, growth stimulants, feeding stimulants, nutrients, hormones, chemosterilants, pheromones, fragrances, flavorants, food additives and combinations thereof and from about 1.0% to about 50% by weight of at least one organic plasticizer coating component wherein said coating component is water soluble or biodegradable or erodible, for regulating the controlled release rate and release profile of said bioactive agent where said plasticizer is an acetate, adipate, azeleate, benzoate, caprylamide, capramide, caprate, citrate, cocoate, fumarate, glutarate, glycolate, heptanoate, isobutyrate, isophthalate, laurate, linoleate, maleate, mellitate, myristate, octanoate, oleate, palmitate, pelargonate, phosphate, phthalate, ricinoleate, sebacate, stearate, succinate, toluate, tallate, decanoate, or epoxidized vegetable oils, a toluamide or chlorinated paraffins, for regulating the controlled release rate and release profile of said bioactive agent said components being selected so that said complex will remain in an application site for a period of time sufficient to effectively treat a population of one or more terrestrial organisms and wherein said composition is free of superabsorbent polymers.
 3. The process of claim 2 wherein said carrier is a hydrophobic or hydrophilic silica, a silicate, diatomaceous earth or sand.
 4. The process of claim 3 wherein said carrier comprises silica having a surface area of from about 50 to about 450 m²/g, an average agglomerate size of from about 3.5 to about 100 μm, or an average primary particle size of from about 12 to about 30 nm, a tapped density of from about 50 to about 240 g/l, a pH from about 3.6 to about 9 and a dibutyl phthalate (DBP) adsorption of from about 160 to about 335 g/100 g.
 5. The process of claim 3 wherein said carrier comprises a silicate having a surface area of from about 30 to about 40 m²/g, an average agglomerate size of from about 4 to about 6 μm, a tapped density of from about 285 to about 315 g/l, a pH of from about 9.5 to about 10.5 and a DBP adsorption of from about 150 to about 170 g/100 g.
 6. The process of claim 2 further comprising a binder.
 7. The process of claim 6 wherein said binder comprises sulfonated polystyrene homopolymers, sulfonated styrene maleic anhydride polymers, sulfonated vinyl toluene maleic anhydride polymers, vinyl pyrrolidone polymers or copolymers, poly(isobutylene-co-disodium maleate) copolymers, acrylamide polymers or copolymers, acrylonitrile-starch graft polymers or copolymers, carboxymethyl-cellulose polymers or copolymers, acrylate polymers or copolymers, poly(vinyl alcohol) polymers or copolymers, poly(ethylene oxide) polymers or copolymers, acrylic acid or acrylic ester homopolymers or copolymers, natural gums, synthetic gums, poly(ethylene glycol), clays, gypsum, plaster, wax, paper, cellulose, latex, methyl vinyl ether maleic acid ester copolymers, starches or modified starches, and combinations thereof.
 8. The process of claim 2 further comprising a joint-function carrier/coating agent.
 9. The process of claim 8 wherein said joint-function carrier/coating agent comprises polyvinyl alcohol, polyethylene oxide, hydroxypropyl methyl cellulose, cetyl alcohol or stearyl alcohol, and combinations thereof.
 10. The process of claim 2 wherein said composition further comprises at least one additional component to further regulate the controlled release rate and release profile of the bioactive agent wherein such components comprise diluents, adjuvants, dyes, alcohols, acetone, ketones, oils, surfactants, water, emulsifiers, film-forming agents, compatibility agents, wetting agents, salt, natural or synthetic polymers, hydrocolloids, buoyancy modifiers, ultraviolet absorbers, photo-protecting agents, suspending agents, elastomers, penetrants, deflocculating agents, dispersing agents, stabilizing agents, antifoaming agents, sticking agents, solvents, co-solvents, catalysts, or synergists, and combinations thereof.
 11. The process of claim 2 comprising delivering said composition as a liquid spray.
 12. The process of claim 2 comprising delivering said composition as a powder, granule, or pellet.
 13. The process of claim 2 comprising delivering said composition as an agglomerate, briquet, extrusion, sheet or film.
 14. The process of claim 2 comprising dispensing said composition from a porous, degradable or soluble container.
 15. The process of claim 2 comprising dispensing said composition from a container with at least one dispensing aperture.
 16. The process of claim 1 or 2 wherein said plasticizer is an acetate.
 17. The process of claim 1 or 2 wherein said plasticizer is an adipate.
 18. The process of claim 1 or 2 wherein said plasticizer is an azeleate.
 19. The process of claim 1 or 2 wherein said plasticizer is a benzoate.
 20. The process of claim 1 or 2 wherein said plasticizer is a caprylamide.
 21. The process of claim 1 or 2 wherein said plasticizer is a capramide.
 22. The process of claim 1 or 2 wherein said plasticizer is a caprate.
 23. The process of claim 1 or 2 wherein said plasticizer is a citrate.
 24. The process of claim 1 or 2 wherein said plasticizer is a cocoate.
 25. The process of claim 1 or 2 wherein said plasticizer is a fumarate.
 26. The process of claim 1 or 2 wherein said plasticizer is a glutarate.
 27. The process of claim 1 or 2 wherein said plasticizer is a glycolate.
 28. The process of claim 1 or 2 wherein said plasticizer is a heptanoate.
 29. The process of claim 1 or 2 wherein said plasticizer is a isobutyrate.
 30. The process of claim 1 or 2 wherein said plasticizer is a isophthalate.
 31. The process of claim 1 or 2 wherein said plasticizer is a laurate.
 32. The process of claim 1 or 2 wherein said plasticizer is a lionleate.
 33. The process of claim 1 or 2 wherein said plasticizer is a maleate.
 34. The process of claim 1 or 2 wherein said plasticizer is a mellitate.
 35. The process of claim 1 or 2 wherein said plasticizer is a myristate.
 36. The process of claim 1 or 2 wherein said plasticizer is a octanoate.
 37. The process of claim 1 or 2 wherein said plasticizer is a oleate.
 38. The process of claim 1 or 2 wherein said plasticizer is a palmitate.
 39. The process of claim 1 or 2 wherein said plasticizer is a pelargonate.
 40. The process of claim 1 or 2 wherein said plasticizer is a phosphate.
 41. The process of claim 1 or 2 wherein said plasticizer is a phthalate.
 42. The process of claim 1 or 2 wherein said plasticizer is a ricinoleate.
 43. The process of claim 1 or 2 wherein said plasticizer is a sebacate.
 44. The process of claim 1 or 2 wherein said plasticizer is a stearate.
 45. The process of claim 1 or 2 wherein said plasticizer is a succinate.
 46. The process of claim 1 or 2 wherein said plasticizer is a toluate.
 47. The process of claim 1 or 2 wherein said plasticizer is a toluamide.
 48. The process of claim 1 or 2 wherein said plasticizer is a tallate.
 49. The process of any one of claims 1, 2, 3-5 and 6-15 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 50. The process of any one of claim 6 or 8 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer, binder and said carrier component.
 51. The process of any one of claim 8 or 9 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer, and joint-function carrier/coating agent, and said carrier component.
 52. The process of claim 10 wherein said composition of matter is a product produced by the process of combining said carrier component, bioactive agent, organic plasticizer, and additional component to further regulate the controlled release rate and release profile of the bioactive agent.
 53. The process of claim 16 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 54. The process of claim 18 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 55. The process of claim 18 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 56. The process of claim 19 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 57. The process of claim 20 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 58. The process of claim 21 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 59. The process of claim 22 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 60. The process of claim 23 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 61. The process of claim 24 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 62. The process of claim 25 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 63. The process of claim 26 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 64. The process of claim 27 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 65. The process of claim 28 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 66. The process of claim 29 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 67. The process of claim 30 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 68. The process of claim 31 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 69. The process of cain 32 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 70. The process of claim 33 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 71. The process of claim 34 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 72. The process of claim 35 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 73. The process of claim 36 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 74. The process of claim 37 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 75. The process of claim 38 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 76. The process of claim 39 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 77. The process of claim 40 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 78. The process of claim 41 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 79. The process of claim 42 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 80. The process of claim 43 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 81. The process of claim 44 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 82. The process of claim 45 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 83. The process of claim 46 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 84. The process of claim 47 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component.
 85. The process of claim 48 wherein said composition of matter is a product produced by the process of combining said bioactive agent, organic plasticizer and said carrier component. 